Hydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethyl piperidyl-1,3,5-triazines) as stabilizers for synthetic polymer compositions

ABSTRACT

Stabilizers for synthetic polymer compositions are provided which are hydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethyl-piperidyl-1,3,5-triazines) having the formula: ##STR1## in which: R is a hydrocarbyl group having the valence n; 
     R 1  is selected from the group consisting of hydrogen; alkyl, alkenyl, cycloalkyl, hydroxyalkyl and alkoxy having from one to about twelve carbon atoms; acyl having from about one to about twelve carbon atoms; and oxyl; 
     Y is selected from the group consisting of ##STR2##  wherein R 4  is lower alkyl having from one to about six carbon atoms; R 5  is selected from the group consisting of hydrogen; alkyl, hydroxy alkyl and alkoxy having from one to about twelve carbon atoms; and cycloalkyl having from three to about twelve carbon atoms; and ##STR3## X is selected from the group consisting of ##STR4## wherein: R 6  is selected from the group consisting of alkyl, hydroxyalkyl and alkylenealkoxy having from one to about twelve carbon atoms; cycloalkyl having from three to about twelve carbon atoms; and aryl having from six to about eighteen carbon atoms; 
     R 7  and R 8  are selected from the group consisting of hydrogen; alkyl having from one to about twelve carbon atoms; cycloalkyl having from three to about twelve carbon atoms; and aryl having from six to about eighteen carbon atoms; and R 7  and R 8  taken together as a five to six member ring including the nitrogen atom in the ring; 
     R 2  and R 3  are selected from the group consisting of hydrogen and lower alkyl having from one to about six carbon atoms; and 
     n is a number from 2 to 4.

Synthetic polymers such as polyethylene, polypropylene and polyvinylchloride undergo degradation upon exposure to ultraviolet light,resulting in discoloration, deterioration in mechanical strength andembrittlement. Consequently, various type of stabilizers have beenincorporated with these polymers to inhibit such deterioration. However,many of the available stabilizers are unsatisfactory in stabilizingeffect, are unstable to heat and subject to oxidation, and are easilyextracted from the synthetic polymer composition by water and organicsolvents. Some of the available stabilizers impart color to the polymercompositions.

Murayama et al. U.S. Pat. No. 3,640,928, patented Feb. 8, 1972,discloses the stabilization of synthetic polymers against photo- andthermo-deterioration thereof by incorporating therein a piperidinederivative having the geneal formula ##STR5##

The 2,2,6,6-tetramethylpiperidyl compounds are particularly desirablebecause they do not impart color, and therefore are widely used.However, these compounds are easily volatilized from the polymercomposition at elevated temperature, such as during processing, and arealso extracted by water. In addition, many are unsatisfactory in theirstabilizing effectiveness.

Triazines containing 2,2,6,6-tetramethyl piperidyl groups have aconsiderably improved heat stability and therefore are preferred formany uses.

Chalmers, Jack and Cook, U.S. Pat. No. 3,925,376 patented Dec. 9, 1975provide piperidinyl 1,3,5-triazine compounds having the formula:##STR6## and salts thereof, wherein U is --CH-- or --N-- and Z' is aresidue having the formula ##STR7## wherein R₁ and R₂ are the same ordifferent and each is a straight- or branched alkyl residue having from1 to 12 carbon atoms, or R₁ and R₂ form, together with the ring carbonatom to which they are each bound, a cycloalkyl residue having from 5 to12 carbon atoms; X is an --O--, --S-- or ##STR8## residue, wherein R ishydrogen, a straight or branched alkyl residue having from 1 to 20carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms; Yis O, hydrogen, a straight or branched alkyl residue having from 1 to 20carbon atoms, an alkenyl or alkynyl residue having from 3 to 12 carbonatoms, an aralkyl residue having from 7 to 12 carbon atoms or the group##STR9## wherein R₈ is hydrogen, or a methyl or phenyl residue; n is 0or 1; and A is --CH₂ --, or the group ##STR10## wherein R₉ is hydrogenor an alkyl residue having from 1 to 20 carbon atoms; Z" and Z"' are thesame or different and each is a piperidine residue of formula II ashereinbefore defined, a halogen atom, a substituted amino group havingthe formula: ##STR11## wherein R₃ and R₄ are the same or different andeach is hydrogen, a straight- or branched alkyl residue having from 1 to20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms,an aryl residue which is unsubstituted or substituted by one or morealkyl groups and having a total of from 6 to 18 carbon atoms or anaralkyl residue having from 7 to 12 carbon atoms; or R₃ and R₄, togetherwith the nitrogen atom to which they are bound form a heterocyclicresidue having 5 to 7 ring atoms; or Z" and Z"' are an hydroxy or ethergroup having the formula:

    --OR.sub.5                                                 IV

wherein R₅ is hydrogen, a straight- or branched-chain alkyl residuehaving from 1 to 20 carbon atoms, a cycloalkyl residue having from 5 to12 carbon atoms, an aryl residue which may be unsubstituted orsubstituted by one or more alkyl groups, having a total of 6 to 18carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms; orZ" and Z"' are a thiol or thio ether group having the formula:

    --SR.sub.6                                                 V

wherein R₆ is hydrogen, a straight- or branched alkyl residue havingfrom 1 to 20 carbon atoms, a cycloalkyl, having from 5 to 12 carbonatoms or a phenyl or benzyl residue.

Cassandrini and Tozzi, U.S. Pat. No. 4,086,204 patented Apr. 25, 1978provide piperidinyl triazine polymers having the general formula:##STR12## in which: X, Y, Z the same or different, represent --O--,##STR13## with R₃ being hydrogen, a straight or branched chain alkylhaving 1 to 18 C atoms, a cycloalkyl having 5 to 18 C atoms, asubstituted or non-substituted aryl having 6 to 18 C atoms, an aralkylhaving 7 to 18 C atoms, or R₃ represents a piperidine radical of theformula: ##STR14## wherein each of R₄, R₅, R₇ and R₈ the same ordifferent, are a C₁ to C₆ alkyl, and R₆ is hydrogen, O, a C₁ to C₁₈straight or branched chain alkyl, a C₂ to C₁₈ alkenyl or alkynyl, or aC₇ to C₁₈ aralkyl;

R₁ is a C₂ to C₁₈ straight or branched chain alkylene, a C₅ to C₁₈cycloalkylene, a C₆ to C₁₈ arylene, and a C₇ to C₁₈ aralkylene.

Furthermore, --X--R₁ --Y-- can be a bivalent radical of a heterocyclecompound with 6 to 8 members having 2 nitrogen atoms; in such case X andY are a disubstituted nitrogen atom respectively;

--X--R₁ --Y-- can be also replaced by the radical ##STR15## in which R₉,R₁₀ the same or different, are H, a C₁ to C₁₂ alkyl, a C₅ to C₁₂cycloalkyl, a C₆ to C₁₂ aryl, a C₇ to C₁₂ aralkyl;

m is either 0 to 1;

R₂ represents --H, --Cl, --Br, --OH, a straight or branched chain C₁ toC₁₈ alkkyl, A C₅ to C₁₈ cycloalkyl, a substituted or not substituted C₆to C₁₈ aryl, a C₇ to C₁₈ aralkyl, a piperidine radical of formula (II),or R₂ represents the radical ##STR16## in which R₁₁, R₁₂ are hydrogen,C₁ to C₁₂ alkyl, C₅ to C₁₂ cycloalkyl, C₆ to C₁₂ aryl, or C₇ to C₁₂aralkyl;

when m is 1, the radical R₂ --Z-- can be the same as --X--R₁ --YH, whereX, Y, R₁ have the meaning above indicated.

n is an integer from 2 to 200;

A and B represent the terminal groups. By the term "terminal groups" itis meant the terminal groups of a molecule of formula (I) resulting fromthe polymerization reaction, which generally are a residue of functionalgroups. The nature of said residue depends on the reaction conditions,the nature and amount of the reactants used in the reaction, forexample, as it is known to one skilled in the art. Said residue ispreferably H for A and --X--R₁ --YH for B, in that it is preferred usingan excess of bifunctional compound in the reaction for controlling themolecular weight.

In formula (I) there is the condition that either radical --X--R₁ --Y--or --(Z)_(m) --R₂, or both contain at least one piperidine radical offormula (II).

Cassandrini and Tozzi, U.S. Pat. No. 4,108,829 patented Aug. 22, 1978,provide piperidinyl 1,3,5-triazine compounds having the general formula(I): ##STR17## wherein R₁, R₂ same or different are hydrogen, hydroxyl,a straight or branched chain C₁ to C₁₈ alkyl, a C₅ to C₁₈ cycloalkyl, asubstituted or not substituted C₆ to C₁₈ aryl, a C₇ to C₁₈ aralkyl, or apiperidine radical of formula (II) ##STR18## in which R₄, R₅, R₇, R₈same or different, are each a C₁ to C₆ alkyl and R₆ is H, O, a C₁ to C₁₂alkyl, a C₂ to C₁₂ alkenyl or alkinyl;

R₁, R₂ can also represent a group ##STR19## in which R₉, R₁₀ same ordifferent, are each hydrogen, C₁ to C₈ alkyl, C₅ to C₈ cycloalkyl or C₆to C₈ aryl;

X, Y same or different represent --O--, --S--, ##STR20## R₁₁ being H, astraight or branched chain C₁ to C₁₈ alkyl, C₅ to C₁₈ cycloalkyl, C₆ toC₁₈ aryl, C₇ to C₁₈ aralkyl, or a piperidine radical of formula (II).

The radicals R₁ --X--, R₂ --Y--, taken as a single substituent group,can also be radicals from nitrogenous heterocyclic compounds having 5 to8 members, linked to the triazine ring by a bisubstituted nitrogen atomof said radical. They can also represent Cl-- or Br--;

n is an integer from 2 to 6;

R₃ is a n-valent residue deriving from a polyalcohol, a polymercaptan ora polyamine by reaction of the active H atoms thereof with a halogenatom of a monohalogen triazine;

R₃ can be a radical of type R₁₂ --(Z)_(n) --, wherein R₁₂ is a n-valent,C₁ to C₁₈ aliphatic, C₅ to C₁₈ cycloaliphatic or C₆ to C₁₈ aromaticradical, and Z is --O--; --S--, ##STR21## wherein R₁₁ has the samemeaning as previously indicated.

When n=2, the radical R₃ can also be the bivalent radical of anitrogenous heterocyclic compound having 6 to 8 members, thebisubstituted nitrogen atoms of which are linked to a triazine ring;when n=2, R₃ can also be a radical of type ##STR22## in which R₁₃, R₁₄same or different, are each hydrogen, C₁ to C₁₂ alkyl, C₅ to C₁₂cycloalkyl, C₆ to C₁₂ aryl, C₇ to C₁₂ aralkyl or a piperidine radical offormula (II).

When n=3, 4, 5, 6, R₃ can also be a radical of type ##STR23## in whichR₁₁ has the same meaning as previously indicated; r, s, same ordifferent, are an integer from 2 to 6 and t is an integer from 0 to 3.

In formula (I) there is the condition that at least in one of theradicals R₁ --X--, R₂ --Y-- and R₃, at least one piperidine radical offormula (II) be present.

Evans and Rasberger, U.S. Pat. No. 4,161,592 patented July 17, 1979,provide piperidine derivatives of 1,3-pyrimidine and 1,3,5-triazinewhich combine a light stabilizing effect and surprisingly goodantioxidative properties in one and the same molecule. Moreover, the newcompounds are distinguished by good color properties.

The compounds correspond to the general formula I ##STR24## or toaddition salts thereof, in which one of the radicals R'; R" and R"'denotes a group of the formula II: ##STR25## wherein one of R₁ and R₃ is--OH and the other is hydrogen, R₂ denotes C₁ -C₁₂ alkyl, C₅ -C₇cycloalkyl, C₆ -C₁₀ aryl or C₇ -C₉ aralkyl, R₄ and R₅ are hydrogen, C₁-C₁₂ alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl or C₇ -C₉ aralkyl, n denotes0 to 12 and X denotes --O--, --S-- or --NR₆ -- wherein R₆ is hydrogen orC₁ -C₁₂ alkyl, and one of the radical R', R" and R"' denotes one of thegroups ##STR26## in which Y is --O-- or --NR₆ -- wherein R₆ has themeaning defined above, Z denotes --O-- or --S--, m is 1 to 6, R₇ ishydrogen or C₁ -C₈ alkyl and R₈ is hydrogen, oxy, C₁ -C₁₂ alkyl, C₃ -C₆alkenyl, C₃ -C₄ alkinyl, C₂ -C₂₁ alkoxyalkyl, C₇ -C₉ aralkyl,2,3-opoxypropyl, an aliphatic acyl group with 1-4 C atoms or one of thegroups --CH₂ COOR₉, --CH₂ --CH(R₁₀)--OR₁₁, --COOR₁₂ or --CONHR₁₂,wherein R₉ is C₁ -C₁₂ alkyl, C₃ -C₆ alkenyl, phenyl, C₇ -C₈ aralkyl orcyclohexyl, R₁₀ is hydrogen, methyl or phenyl, R₁₁ denotes hydrogen, analiphatic, aromatic, araliphatic or alicyclic acyl group with 1-18 Catoms, wherein the aromatic part, if appropriate, can be substituted bychlorine, C₁ -C₄ alkyl, C₁ -C₈ alkoxy and/or by hydroxyl, and R₁₂denotes C₁ -C₁₂ alkyl, cyclohexyl, phenyl or benzyl, and R₁₃ denoteshydrogen, --OH or one of the groups --O--CO--R₁₄ or --NR₁₂ --CO--R₁₄,wherein R₁₄ denotes C₁ -C₁₂ alkyl or phenyl, and one of the radicals R',R" and R"' independently of the others denotes an identical or differentgroup of the formula II, or denotes an identical or different group III,IV or V, or denotes --N₃ or one of the groups --S--R₁₅, --OR₁₇,--P(O)--(OR₁₇)₂ or --NR₁₃ R₁₉, wherein R₁₅ denotes hydrogen, C₁ -C₁₈alkyl, C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₉ aralkyl or the group--(C_(p) H.sub. 2p)--CO--OR₁₆ wherein R₁₆ is C₁ -C₁₈ alkyl and p denotes1 to 6, R₁₇ denotes C₁ -C₁₈ alkyl, C₆ -C₁₀ aryl or C₇ -C₉ aralkyl andR₁₈ and R₁₉ independently of one another denote hydrogen, C₁ -C₁₃ alkyl,C₅ -C₇ cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₉ aralkyl or the group ##STR27##in which R₇ and R₈ have the meaning defined above.

Rody and Berner, U.S. Pat. No. 4,234,728 patented Nov. 18, 1980, provides-triazine derivatives which contain, as substituents in the 2-, 4- and6-position, at least one polyalkylpiperidine radical and at least oneN-methylolamino group, or the ethers thereof. These compounds can bemono- or polytriazines, and have the formula I or II ##STR28## in whichm is an integer from 1 to 4 and n is a value from 2 to 50, X and X' are--O--, --S-- or --NR⁶ --, in which R⁶ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₈alkenyl, C₁ -C₄ hydroxyalkyl, C₂ -C₁₃ alkoxyalkyl, C₅ -C₁₂ cycloalkyl,C₆ -C₁₀ aryl, C₇ -C₉ phenylalkyl or a polyalkyl piperidine group of theformula III ##STR29## in which R is hydrogen or methyl, p is 0 or 1, Ais C₁ -C₄ alkylene, --NR⁶ --C₂ --C₁₂ alkylene or --OCH₂ CH₂ CH₂ -- and Ris H, O, C₁ -C₁₂ alkyl, allyl, benzyl or a --CH₂ CH(R⁸)--OH group, inwhich R⁸ is H, CH₃, C₂ H₅ or phenyl, and R¹ and R³ are hydrogen, C₁ -C₁₈alkyl, C₃ -C₈ alkenyl, C₁ -C₄ hydroxyalkyl, C₂ -C₁₃ alkoxyalkyl, C₅ -C₁₂cycloalkyl, C₆ -C₁₀ aryl, C₇ -C₉ phenylalkyl, phenyl or phenylalkylwhich is substituted by 1 to 2 C₁ -C₈ alkyl groups and/or OH and/or C₁-C₄ alkoxy, or a polyalkylpiperidine group of the formula III, R₂ ishydrogen, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₂ -C₆ hydroxyalkyl or C₃ -C₆alkoxyalkyl, R₄, if m is 1, is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl,C₂ -C₄ hydroxyalkyl, C₃ -C₆ alkoxyalkyl, C₅ -C₁₀ aryl, C₇ -C₉phenylalkyl, phenyl or phenylalkyl which is substituted by 1 or 2 C₁ -C₈alkyl groups and/or OH and/or C₁ -C₄ alkoxy, or a polyalkylpiperidinegroup of the formula III, and if m is 2 is C₂ -C₁₂ alkylene oroxaalkylene, C₄ -C₁₂ alkenylene, C₆ -C₁₀ arylene, aphenylene-Z-phenylene-radical, in which Z is --O--, --S--, --SO₂ --,--CH₂ -- or --C(CH₃)₂ -- or a radical of the formula --(CH₂)_(r)--NY--(CH₂)_(r) --NY_(q) --(CH₂)_(r) --, wherein r is 2 or 3 and q is 0or 1 and Y is a triazinyl group of the formula IV, ##STR30## and if m is3 is a R³ --C(CH₂ --)₃ radical, in which R⁸ is C₁ -C₄ alkyl, and if m is4 is a C(CH₂ --)₄ radical, R⁵ is C₂ -C₁₂ alkylene and E and E' arecorresponding end groups and at least one of the radicals R¹, R³, R⁴ orR⁵ is a piperidine radical of the formula III.

Cassandrini and Rozzi, U.S. Pat. No. 4,263,434 patented Apr. 21, 1981,provides piperidyltriazine derivatives which are useful for improvingthe stability to light, heat and oxidation of polymeric substances, andwhich have the general formula (I): ##STR31## wherein R₁, R₂ same ordifferent are hydrogen, hydroxyl, a straight or branched chain C₁ to C₁₈alkyl, a C₅ to C₁₈ cycloalkyl, a substituted or not substituted C₆ toC₁₈ aryl, a C₇ to C₁₈ aralkyl, or a piperidine radical of formula (II)##STR32## in which R₄, R₅, R₇, R₈ same or different, are each a C₁ to C₆alkyl and R₆ is H, O, a C₁ to C₁₂ alkyl, a C₂ to C₁₂ alkenyl or alkinyl;

R₁, R₂ can also represent a group ##STR33## in which R₉, R₁₀ same ordifferent, are each hydrogen, C₁ to C₈ alkyl, C₅ to C₈ cycloalkyl or C₆to C₈ aryl;

X, Y same or different represent --O--; --S--, ##STR34## R₁₁ being H, astraight or branched chain C₁ to C₁₈ alkyl, C₅ to C₁₈ cycloalkyl, C₆ toC₁₈ aryl, C₇ to C₁₈ aralkyl, or a piperidine radical of formula (II).

The radicals R₁ --X--, R₂ --Y--, taken as a single substituent group,can also be radicals from nitrogenous heterocyclic compounds having 5 to8 members, linked to the triazine ring by a bisubstituted nitrogen atomof said radical.

They can also represent Cl-- or Br--;

n is an integer from 2 to 6;

R₃ is a n-valent residue deriving from a polyalcohol, a polymercaptan ora polyamine by reaction of the active H atoms thereof with a halogenatom of a monohalogen triazine;

R₃ can be a radical of type R₁₂ --(Z)_(n) --, wherein R₁₂ is a n-valent,C₁ to C₁₈ aliphatic, C₅ to C₁₈ cycloaliphatic or C₆ to C₁₈ aromaticradical, and Z is --O--, --S--, ##STR35## wherein R₁₁ has the samemeaning as previously indicated.

When n=2, the radical R₃ can also be the bivalent radical of anitrogenous heterocyclic compound having 6 to 8 members, thebisubstituted nitrogen atoms of which are linked to a triazine ring;when n=2, R₃ can also be a radical of type ##STR36## in which R₁₃, R₁₄,same or different, are each hydrogen, C₁ to C₁₂ alkyl, C₅ to C₁₂cycloalkyl, C₆ to C₁₂ aryl, C₇ to C₁₂ aralkyl or a piperidine radical offormula (II).

When n=3, 4, 5, 6, R₃ can also be a radical of type ##STR37## in whichR₁₁ has the same meaning as previously indicated; r, s, same ordifferent, are an integer from 2 to 6 and t is an integer from 0 to 3.

In formula (I) there is the condition that at least in one of theradicals R₁ --X--, R₂ --Y-- and R₃, at least one piperidine radical offormula (II) be present.

Rody, U.S. Pat. No. 4,288,593, patented Sept. 8, 1981, providespolyalkylpiperidine derivatives of s-triazines of the formula ##STR38##in which X and X' are a divalent organic radical, X", X₁ AND X₂ are adirect bond or a divalent organic radical, Y, Y', Y", Y₁, Y₂, Z and Z'are --O--, --S--, --NH-- or --NR³ --, R is H or CH₃ and R¹, R² and R³are a monovalent organic radical or a polyalkylpiperidine group, or thegroup R¹ --X"--Y"-- is chlorine, and R⁴ is H, O, alkyl, allyl or benzyl.These are stabilizers for polymeric materials, in particular to protectthem against photochemical degradation.

Nikles, U.S. Pat. No. 4,315,859 patented Feb. 16, 1982, providespolymeric polyamine-1,3,5-triazines which have an excellent stabilizingaction, of the general formula I ##STR39## wherein the symbols which mayor may not recur in the compound, and which on each possible recurrencecan be the same or different, are defined as follows: X is C₂ -C₆alkylene, A is --O--, --S-- or --NR--, wherein R, which is alsorecurring or non-recurring and on each possible recurrence can be thesame or different, is hydrogen, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆-C₁₀ aryl or the radical of the formula II ##STR40## wherein R³ ishydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₂ alkenyl, C₃ -C₅ alkynyl, C₃ -C₁₈alkoxyalkyl, C₂ -C₄ hydroxyalkyl which is unsubstituted or substitutedby phenyl or phenoxy, or C₇ -C₁₈ aralkyl, and R⁴ is hydrogen or methyl,or R is also one or more of the structural units contained with thebrackets of formula I, said structural unit or units being terminallysaturated by U and being bound through a triazine C atom, and wherein Rand R¹ as end groups, each independently of the other, can be hydrogen,C₁ -C₂₃ alkyl which can be interrupted by oxygen, C₃ -C₁₂ cycloalkyl, C₇-C₁₈ aralkyl, C₆ -C₁₀ aryl or the radical of the formula II, and R¹ asend group can also in addition be a group of the formula III

    (X--A).sub.p X--NR.sup.5 R.sup.6                           (III)

wherein R⁵ and R⁶, each independently of the other, are U, C₁ -C₂₃ alkylwhich can be interrupted by oxygen, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl,C₆ -C₁₀ aryl, the radical of the formula II or a group of the formula IV

    (X--A).sub.p X--N(R).sub.2                                 (IV)

R² is halogen cyano, azido, hydrazido, phenyl, --OR⁷, --SR⁷ or --NR⁸ R⁸', wherein R⁷ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₂ alkenyl, C₃ -C₁₈alkoxyalkyl, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl, or theradical of the formula II, and R⁸ and R⁸ ', each independently of theother, are hydrogen, C₁ -C₂₃ alkyl which can be interrupted by oxygen,C₃ -C₁₈ alkenyl, C₃ -C₅ alkynyl, C₂ -C₁₀ hydroxyalkyl, C₂ -C₅cyanoalkyl, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl or theradical of the formula II, or R⁸ and R⁸ ' together with the nitrogenatom to which they are attached form a pyrrolidine ring or a piperidine,morpholine or hexamethyleneimine ring which is unsubstituted orsubstituted by C₁ -C₄ alkyl, or R² on each of its possible recurrencescan also be a radical of the formula V ##STR41## wherein a can be 0, 1,2, 3 or 4, or a radical of the formula VI ##STR42## wherein q can be 0,1 or 2 and r can be 0, 1, 2 or 3, whilst the sum of r+q may not be morethan 3, or R² can also be one or more of the structural units containedwith the brackets of formula I, said structural unit or units beingterminally saturated by Q and being bound through the amine nitrogenatom, and wherein R² as end group is halogen, phenyl, --OR⁷, --SR⁷,--NR⁸ R⁸ ', a group of the formula VII, ##STR43## or of the formula VIII##STR44## wherein A¹ is --O--, --S-- or --NR⁵, whilst Q is halogen,--NR⁸ R⁸ ', --OH, --OMe/b, wherein Me/b represents an alkali metal oralkaline earth metal of the valency b, and b is 1 or 2, or Q is aradical of the formula VII or VIII, U is hydrogen, a group of theformula ##STR45## or C₁ -C₂₄ acyl, and n can be an integer from 1 to100, with the priviso that at least one R, one R¹ or one R² is orcontains a group of the formula II and, if m is 0, at least one R¹ mustbe a group of the formula III or IV.

Rody, U.S. Pat. No. 4,294,963, patented Oct. 13, 1981, providespolyalkylpiperidine derivatives of s-triazines as stabilizers forpolymers. The compounds have the formula I or II ##STR46## wherein m is2, 3 or 4, n is 2 to 50, p is 0 or 1, X, X' and X" represent a directbond, C₁ -C₄ alkylene or --OCH₂ CH₂ CH₂ --, the O of which is not bondedto Y, Y' or Y"; Y, Y', Y" and Y'" represent --O--, --S--, --NH-- or--NR³ --, Z represents C₂ -C₁₂ alkylene, C₄ -C₂₀ alkylene interrupted by--O--, --S--, --NH-- or --NR³ --, xylene, C₆ -C₁₂ arylene or phenyleneQ' phenylene, wherein Q' is --CH₂ --, >C(CH₃)₂, --SO₂ -- or --O--, Rrepresents hydrogen or C₁ -C₄ alkyl, R¹, R² and R³ represent C₁ -C₁₂alkyl, C₂ -C₈ alkoxyalkyl, C₂ -C₄ hydroxyalkyl, C₅ -C₁₂ cycloalkyl, C₇-C₁₂ aralkyl, C₃ -C₁₈ alkenyl, C₆ -C₁₀ aryl, phenyl which is substitutedby one or two C₁ -C₈ alkyl groups and/or by OH and/or by C₁ -C₄ alkoxy,or represent a polyalkylpiperidinyl group of the formula III ##STR47##or, if Y' or Y" is --NR³ -- and X' or X" is a direct bond, R¹ and R²together with the nitrogen atom form a pyrrolidone, piperidine ormorpholine ring,

R⁴ represents hydrogen, O, C₁ -C₁₂ alkyl, allyl or benzyl,

A if m is 2, represents C₂ -C₁₂ alkylene, C₄ -C₈ alkylene, xylylene or aradical of the formula --CH₂ --C.tbd.C--CH₂ --, ##STR48## --CH₂--COO--R⁵ --OOC--CH₂, --CH₂ --CH(OH)--CH₂ -- or --CH₂ CH(OH)CH₂ --D--CH₂CH(OH)CH₂ --, or if m is 3, represents a group of the formula ##STR49##and, if m is 4, represents a group of the formula ##STR50## B representsC₂ -C₁₂ alkylene, C₄ -C₈ alkenylene, xylylene or a radical of theformula --CH₂ --COO--R⁵ --OOC--CH₂, --CH₂ --CH(OH)--CH₂ or --CH₂CH(OH)CH₂ --D--CH₂ CH(OH)CH₂,

R⁵ represents C₂ -C₈ alkylene, C₄ -C₈ oxaalkylene or cyclohexylene,

D represents a divalent radical of the formula --O--R⁶ --O--,--O--C(O)--R⁷ --C(O)--O--, --OCH(R³)CH₂ O--R⁶ --OCH₂ CH(R⁸)O-- or##STR51## R⁶ represents C₂ -C₁₂ alkylene, C₆ -C₁₂ cycloalkylene, C₆ -C₁₂arylene or phenylene Z₁ phenylene, wherein Z₁ represents --CH₂ --,>C(CH₃)₂, --SO₂ -- or --O--,

R⁷ represents a direct bond, C₁ -C₁₂ alkylene, C₂ -C₆ alkenylene, C₆-C₁₂ cycloalkylene or cycloalkenylene or C₆ -C₁₂ arylene,

R⁸ and R⁹ are hydrogen or C₁ -C₄ alkyl,

T represents a trivalent radical of the formulae ##STR52## R¹⁰represents a trivalent aliphatic hydrocarbon radical of 3 to 10 carbonatoms,

Q represents a quadrivalent radical of the formula ##STR53## R¹¹represents a quadrivalent aliphatic hydrocarbon radical of 4 to 10carbon atoms, and

E and E' represent end groups.

Sankyo and Ciba-Geigy British Pat. No. 1,496,454 discloses 3- or5-substituted 2,2,6,6-tetra-4-piperidinol derivatives of the generalformula: ##STR54##

In this formula, R^(a) and R^(b) may be hydrogen, but one must be loweralkyl, alkenyl or alkynyl, so that a 3- or 5-substituent is necessary.

Y is a mono to tetravalent organic group, and X can be hydrogen.

Various types of Y groups are illustrated at page 6, column 1, includinga group of formula ##STR55## which is 1,3,5-triazine.

The Sankyo British patent also indicates in the summary of prior art atpage 2, column 1, that German Offenlegungsschrift No. 2,319,816discloses 2,4,6-tri(piperidyl-4-oxy-1,3,5-triazine derivatives.

Rasberger and Karrer, U.S. Pat. No. 4,317,911, patented Mar. 2, 1982,discloses piperidinyl isocyanurates having the general formula:##STR56## and to addition salts thereof, in which R₁ denotes ##STR57##

These compounds have the piperidinyl group attached to the isocyanuratenucleus by way of a ##STR58## linking group, where X can be oxygen.

Morimura, Toda and Kurumada, U.S. Pat. No. 4,321,374 patented Mar. 23,1982, provides s-triazine derivatives having the formula ##STR59##wherein R₁ represents hydrogen atom or methyl group,

R₂ represents hydrogen atom, an alkanoyl group having from 2 to 18carbon atoms or 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl group,

n is 1 or 2,

when n is 1,

X represents an alkyl group having from 1 to 18 carbon atoms, benzylgroup or a group of the formula --CH₂ CH₂ OR₂ (wherein R₂ is as definedabove) and

Y represents hydrogen atom, a group of the formula ##STR60## or a groupof the formula ##STR61## (wherein R₁ and R₂ are as defined above), whenn is 2,

X represents an alkylene group having from 2 to 6 carbon atoms, xylylenegroup or a group of the formula ##STR62## (wherein m is an integer from1 to 4 and Z represents a group of the above formula (III)) and

Y represents hydrogen atom or a group of the above formula (II).

In the formula (I), R₂ as an alkanoyl group having from 2 to 18 carbonatoms can be, for example, acetyl, propionyl, butyryl, hexanoyl,octanoyl, lauroyl, palmitoyl or stearoyl, in particular, it is desirablyan alkanoyl group having from 2 to 4 carbon atoms. X as an alkyl grouphaving from 1 to 18 carbon atoms can be a straight or branched chainalkyl, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tert-butyl, hexyl, octyl, 2-ethylhexyl, tert-octyl, decyl, dodecyl,tetradecyl or octadecyl, in particular, it is desirably an alkyl grouphaving from 8 to 18 carbon atoms. X as an alkylene group having from 2to 6 carbon atoms can be, for example, 1,2-ethylene, 1,2-propylene,1,4-butylene or 1,6-hexylene, desirably 1,6-hexylene.

Preferred compounds of the formula (I) are those in which R₁ is hydrogenatom or R₂ is hydrogen atom. More preferred compounds of the formula (I)are those in which

(1) R₁ and R₂ are hydrogen atoms, n is 1, X is an alkyl group havingfrom 8 to 10 carbon atoms and Y is hydrogen atom or2,4-bis[2-hydroxy-N-(2,2,6,6-tetramethyl-4-piperidyl)ethylamino]-1,3,5-triazine-6-ylgroup;

(2) R₁ and R₂ are hydrogen atom, n is 1, X is 2-hydroxyethyl group and Yis 2,2,6,6-tetramethyl-4-piperidyl group;

(3) R₁ and R₂ are hydrogen atom, n is 2, X is 1,6-hexylene group or agroup of the formula ##STR63## (wherein m is an integer from 1 to 4 andZ is2,4-bis[2-hydroxy-N-(2,2,6,6-tetramethyl-4-piperidyl)e-thylamino]-1,3,5-triazine-6-ylgroup) and Y is hydrogen atom.

U.K. patent application No. 2,117,377 published Oct. 12, 1983 disclosespiperidine derivatives that have the general formula ##STR64## where Rdenotes hydrogen, alkyl, cycloalkyl, alkenyl, aralkyl or aryl; R₁ andR'₁ denote hydrogen, alkyl, alkenyl or aralkyl;

R₂ and R'₂ denote hydrogen or methyl;

X and X' denote oxygen or NR₃ ;

R₃ denotes hydrogen, alkyl, cycloalkyl or aralkyl;

A and A' denote (CH₂)_(m) X";

m equals 2 or 3;

X" has the same meaning as X and X', and

n can be 0 or 1.

These are used as stabilizers for polymers.

U.S. Pat. No. 4,500,663, patented Feb. 19, 1985, providesN,N,N-tris(2,2,6,6-tetramethyl-4-piperidone ketal)-1,3,5-triazineshaving the formula: ##STR65## wherein: R₁ is selected from the groupconsisting of hydrogen and alkyl having from one to about four carbonatoms; and

R₂ is selected from the group consisting of hydrogen; oxyl O; alkyl,hydroxy alkyl and epoxyalkyl having from one to about eighteen carbonatoms; acyl having from one to about eighteen carbon atoms; cycloalkylhaving from three to about eighteen carbon atoms; phenyl; phenalkyl andalkylphenyl having from seven to about twenty-four carbon atoms; as wellas synthetic resin compositions having an improved resistance todeterioration and containing such compounds.

U.S. Pat. No. 4,540,728, patented Sept. 10, 1985, provides polymers ofdiallyl-1,3,5-triazino-4-(2,2,6,6-tetramethyl piperidyl)amines having amolecular weight within the range from about 800 to about 20,000, andderived from the monomer: ##STR66## wherein: R₁ is selected from thegroup consisting of hydrogen; oxyl; alkyl and hydroxyalkyl having fromone to about eighteen carbon atoms; alkylaryl having from seven to abouteighteen carbon atoms; epoxy alkyl having from three to about eighteencarbon atoms; and acyl having from two to about eighteen carbon atoms;

Y is selected from the group consisting of ##STR67## where R₂ and R₃ arehydrogen or alkyl having from one to about eight carbon atoms and n is 0or 1;

Z is selected from the group consisting of ##STR68## in which R₄, R₅ andR₆ are selected from the group consisting of hydrogen; alkyl having fromone to about eighteen carbon atoms; cycloalkyl having from three toabout twelve carbon atoms; and aryl having from six to about thirtycarbon atoms; as well as stabilized synthetic resin compositions havingan improved resistance to deterioration by light and containing such apolymer.

U.S. Pat. No. 4,491,643, patented Jan. 1, 1985, providesbis(2,2,6,6-tetramethylpiperidyl-1,3,5-triazinyl)spirodiamines andspiroglycol ethers having the formula: ##STR69## wherein: R₁ is selectedfrom the group consisting of hydrogen, alkyl having from one to abouteighteen carbon atoms, hydroxyalkyl having from two to about six carbonatoms; epoxyalkyl having from three to about eight carbon atoms;alkylaryl having from seven to about eighteen carbon atoms; acyl havingfrom two to about eight carbon atoms; and oxyl;

R₂ is alkylene having from one to about six carbon atoms;

Z is selected from the group consisting of ##STR70## in which R₃ isalkyl having from one to about six carbon atoms; and R₄ is selected fromthe group consisting of hydrogen; alkyl having from one to abouteighteen carbon atoms; cycloalkyl having from about four to about eightcarbon atoms; hydroxy alkyl and alkoxyalkyl having from two to abouttwelve carbon atoms and dialkylamino having from two to about ten carbonatoms;

X is selected from the group consisting of --O-- and ##STR71## in whichR₅ is selected from the group consisting of hydrogen, alkyl having fromone to about eighteen carbon atoms; cycloalkyl having from about four toabout eight carbon atoms; hydroxy alkyl and alkoxyalkyl having from twoto about twelve carbon atoms, and dialkylamino having from two to aboutten carbon atoms; and ##STR72## Y is selected from the group consistingof: ##STR73## and Cl; in which R₆ is selected from the group consistingof alkyl having from one to about eighteen carbon atoms; cycloalkylhaving from about four to about eight carbon atoms; hydroxy alkyl andalkoxyalkyl having from two to about twelve carbon atoms anddialkylamino having from two to about ten carbon atoms and aryl andalkaryl having from six to about twenty-four carbon atoms;

R₇ and R₈ are selected from the group consisting of hydrogen, alkylhaving from one to about eighteen carbon atoms; and alkylene forming aheterocyclic ring including the nitrogen atom in the ring and havingfrom four to seven carbon atoms and no or one oxygen atom; and

n is a number from 1 to about 50 representing the average number ofunits enclosed by the brackets; and synthetic resin compositionscontaining the same as light stabilizers.

Additional patents disclosing such compounds include Rody U.S. Pat. No.4,288,593, Morimura et al. U.S. Pat. No. 4,322,527 and Japan Kokai Nos.67749/78 and 102637/80.

The Cassandrini et al. compounds having more than 2 triazine ringsderived from polyamines or polyols have an exceptionally good heatstability and low extractability, but the stabilizing effect of thesecompounds is not fully satisfactory.

In accordance with the present invention, hydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethyl-piperidyl-1,3,5-triazines) areprovided having the formula: ##STR74## in which: R is a hydrocarbylgroup having the valence n;

R₁ is selected from the group consisting of hydrogen; alkyl, alkenyl,cycloalkyl, hydroxyalkyl and alkoxy having from one to about twelvecarbon atoms; acyl having from about one to about twelve carbon atoms;and oxyl;

Y is selected from the group consisting of ##STR75## wherein R₄ is loweralkyl having from one to about six carbon atoms; R₅ is selected from thegroup consisting of hydrogen; alkyl, hydroxy alkyl and alkoxy havingfrom one to about twelve carbon atoms; and cycloalkyl having from threeto about twelve carbon atoms; and ##STR76## X is selected from the groupconsisting of ##STR77## wherein: R₆ is selected from the groupconsisting of alkyl, hydroxyalkyl and alkylenealkoxy having from one toabout twelve carbon atoms; cycloalkyl having from three to about twelvecarbon atoms; and aryl having from six to about eighteen carbon atoms;

R₇ and R₈ are selected from the group consisting of hydrogen; alkylhaving from one to about twelve carbon atoms; cycloalkyl having fromthree to about twelve carbon atoms; and aryl having from six to abouteighteen carbon atoms; and R₇ and R₈ taken together as a five to sixmember ring including the nitrogen atom in the ring;

R₂ and R₃ are selected from the group consisting of hydrogen and loweralkyl having from one to about six carbon atoms; and

n is a number from 2 to 4.

These compounds have an improved stabilizing effectiveness as comparedto previous compounds of this type, and impart to synthetic polymercompositions a considerably improved resistance to deterioration uponexposure to ultraviolet light.

The R hydrocarbyl groups are selected from the group consisting ofalkylene, alkylidene, cycloalkylene, cycloalkylidene, arylene andarylidene hydrocarbon groups having from one to about eighteen carbonatoms.

Exemplary R alkylene groups include methylene; ethylene; 1,2-propyleneand 1,3-propylene; butylene, including 1,2-butylene, 2,3-butylene,2,4-butylene and 1,4-butylene; pentylene, including 1,5-pentylene,1,3-pentylene, 1,4-pentylene, 1,2-pentylene and 2,4-pentylene; hexylene,including 1,6-hexylene, 1,2-hexylene, 1,3-hexylene, 1,4-hexylene,1,5-hexylene, 2,3-hexylene, 2,4-hexylene and 2,5-hexylene; heptylene,including 1,7-heptylene, 1,2-heptylene, 1,3-heptylene, 1,4-heptylene,1,5-heptylene, 2,6-heptylene, 2,3-heptylene, 2,4-heptylene,3,5-heptylene, and 3,4-heptylene; octylene, including 1,8-octylene,1,2-octylene, 1,3-octylene, 1,4-octylene, 1,5-octylene, 2,7-octylene and2,4-octylene; nonylene, including 1,9-nonylene, 2,7-nonylene, and2,5-nonylene; decylene, including 1,10-decylene, 2,4-decylene,2,5-decylene and 2,8-decylene; undecylene, including 1,11-undecylene,2,10-undecylene, 3,5-undecylene and 4,8-undecylene; and dodecylene,including 1,12-dodecylene, 2,11-dodecylene, 2,4-dodecylene, and3,6-dodecylene.

Exemplary R cycloalkylene include cyclopropylene, cyclobutylene,cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene andcyclododecylene.

Exemplary R arylene include phenylene, tolylene, mesitylylene, andxylylene.

Exemplary R alkylidene include methylidene, ethylidene, isopropylidene,butylidene, isobutylidene, pentylidene, isopentylidene, hexylidene,isohexylidene, heptylidene, octylidene, nonylidene, decylidene,undecylidene and dodecylidene.

Exemplary R cycloalkylidene include cyclopropylidene, cyclobutylidene,cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene andcyclododecylidene.

Exemplary R arylidene include phenylidene, tolylidene and xylylidene.

Exemplary R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ alkyl include methyl, ethyl,propyl, isopropyl, butyl, isobutyl, tertiary-butyl, secondary-butyl,amyl, isoamyl, secondary-amyl, tertiary-amyl, hexyl, isohexyl,tertiary-hexyl, heptyl, isoheptyl, secondary-heptyl, octyl, isooctyl,2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, dodecyl, isododecyl,hexadecyl and octadecyl.

Exemplary R₁, R₅, R₆, R₇ and R₈ hydroxyalkyl include 2-hydroxyethyl,2-hydroxypropyl, 4-hydroxybutyl, 2,3-dihydroxy butyl, 6-hydroxy hexyl,12-hydroxy dodecyl.

Exemplary R₁, R₅, R₆, R₇ and R₈ alkoxy include methoxy, ethoxy, propoxy,butoxy, amyloxy, hexoxy, heptoxyl, decoxy, dodecoxy, methoxyethyl,butoxyethyl, 2,3-epoxypropyl, ethoxydecyl, and propoxypropyl.

Exemplary R₁ alkenyl include allyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, decenyl, and dodecenyl.

Exemplary R₁ acyl include acetyl, propionyl, butyroyl, acryloyl,methacryloyl, octanoyl and benzoyl.

Exemplary R₁, R₅, R₆, R₇ and R₈ cycloalkyl include cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl andcyclododecyl.

Exemplary R₆, R₇ and R₈ aryl include phenyl, naphthyl, tolyl, xylyl,mesityl, tertiary-butylphenyl, octylphenyl, 2,4-di-tertiary-butylphenyl,nonylphenyl and dinonylphenyl.

Exemplary five- and six-member rings formed with R₇, R₈ and the nitrogenatom include pyrollidino, piperidino, morpholino and methylpiperidino.

Exemplary X alkylamino include dimethylamino, diethylamino, methylcyclohexylamino, dipropylamino, and dicyclohexylamino.

The following compounds are exemplary: ##STR78##

These compounds are easily prepared by known procedures, reactingcyanuric chloride with the corresponding 2,2,6,6-tetramethyl piperidinecompound, followed by reaction with the corresponding hydrocarbylpolyphenol. Polyphenols useful as raw materials for preparing thesecompounds include 4,4'-isopropylidenediphenol, 4,4'-methylenediphenol,4,4'-methylenebis(2,6-dimethylphenol),4,4'-butylidenebis(3-methyl-6-t-butylphenol),1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)-3-phenylpropane, and1,1,5,5-tetra(4-hydroxyphenyl)pentane and1,1,5,5-tetra(2-methyl-4-hydroxyphenyl)pentane.

The following Examples illustrate the procedure.

EXAMPLE I

Preparation of ##STR79##

4,4'-Isopropylidenebisphenol, 1.71 g, 28% sodium methoxide solution inmethanol, 2.90 g, sodium iodide, 0.48 g, and diethyleneglycol diethylether, 30 ml, were mixed and stirred for 30 minutes at 80° C. Then2-chloro-4,6-bis(N-2,2,6,6-tetramethyl-4piperidyl)butylamino)-1,3,5-triazine,8.03 g, was added, and the mixture stirred for 20 hours under reflux.Then the reaction was stopped by distilling off the solvent. 50 ml ofbenzene was added, the solution washed with water, and then dried. Thesolvent was distilled off, and the product purified by passage through asilica gel column using methanol/acetone as the solvent. The product wasa glassy solid melting at 108°-112° C.

EXAMPLE II

Preparation of ##STR80##

1,1,3-Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1.82 g, sodiummethoxide 28% solution in methanol, 1.93 g, sodium iodide, 0.36 g, anddiethyleneglycol diethyl ether, 20 ml, were mixed and stirred for 30minutes at 80° C. Then2-chloro-4,6-bis((N-2,2,6,6-tetramethyl-4-piperidyl)butylamino)1,3,5-triazine, 5.36 g, was added, and the mixture stirred for 20 hoursunder reflux. The product was isolated by distilling off the solvent. 50ml of benzene was added, and the solution washed with water and dried.The solvent was then distilled off, and the product purified by passagethrough a silica gel column, using methanol/acetone as the solvent. Theproduct obtained was a glassy solid, melting at 143°-147° C.

The hydrocarbyl(polyphenol) poly(piperidyl triazines) of this inventionare effective light stabilizers for polymeric materials that are subjectto deterioration when exposed to light. Small amounts are effective. Anamount within the range from about 0.001 to about 5 parts, preferablyfrom 0.01 to 3 parts, by weight per 100 parts by weight of polymer isusually sufficient. Larger amounts can be used, if desired.

Synthetic resins that can have their resistance to deteriorationenhanced with the hydrocarbyl(polyphenol) poly(piperidyl triazines)according to this invention include α-olefin polymers such aspolyethylene, polypropylene, polybutene, poly-3-methylbutene, ormixtures thereof, and copolymers with other monomers such asethylene-vinyl acetate copolymer; ethylene-propylene copolymer;polystyrene; polyvinyl acetate; polyacrylic esters; copolymers fromstyrene and another monomer (for example, maleic anhydride, butadiene,and acrylonitrile); acrylonitrile-butadiene-styrene copolymer, acrylicacid ester-butadiene-styrene copolymer, methacrylic acidester-butadiene-styrene copolymer, polymethacrylate esters such aspolymethacrylate; polyvinyl alcohol; polyvinyl formal; polyvinylbutyral; linear polyesters, polyamides; polycarbonates; polyacetals;polyurethanes; cellulosic resins; phenol-formaldehyde resins;urea-formaldehyde resins; melamine-formaldehyde resins; epoxy resins;unsaturated polyester resins; silicone resins; halogen-containing resinssuch as polyvinyl chloride, polyvinylidene chloride, polyvinylidenefluoride, and copolymers thereof, and rubbers such as isoprene rubber,butadiene rubber, epichlorohydrin rubber, chloroprene rubber, and blendsof any of the above.

The hydrocarbyl(polyphenol) poly(piperidyl triazines) of the inventioncan be combined with conventional heat stabilizers such as phenolicantioxidants, polyvalent metal salts of organic acids, organicphosphites, thioethers, and other known heat stabilizers, therebyconstituting light and heat stabilizer compositions of the invention.

The phenolic antioxidant contains one or more phenolic hydroxyl groups,and one or more phenolic nuclei, and can contain from about eight toabout three hundred carbon atoms. In addition, the phenolic nucleus cancontain an oxy or thio ether group.

The alkyl-substituted phenols and polynuclear phenols, because of theirmolecular weight, have a higher boiling point, and therefore arepreferred because of their lower volatility. There can be one or aplurality of alkyl groups of one or more carbon atoms. The alkyl groupor groups including any alkylene groups between phenol nuclei preferablyaggregate at least four carbon atoms. The longer the alkyl or alkylenechain, the better the compatibility with polypropylene, inasmuch as thephenolic compound then acquires more of an aliphatic hydrocarboncharacter, and therefore there is no upper limit on the number of alkylcarbon atoms. Usually, from the standpoint of availability, the compoundwill not have more than about eighteen carbon atoms in an alkyl,alicyclidene and alkylene group, and a total of not over about fiftycarbon atoms. The compounds may have from one to four alkyl radicals perphenol nucleus.

The phenol contains at least one and preferably at least two phenolichydroxyls, the two or more hydroxyls being in the same ring, if there isonly one. In the case of bicyclic phenols, the rings can be linked bythio or oxyether groups, or by alkylene, alicyclidene or arylidenegroups.

The monocyclic phenols which can be employed have the structure:##STR81## R is selected from the group consisting of hydrogen; halogen;and organic radicals containing from one to about thirty carbon atoms,such as alkyl, aryl, alkenyl, alkaryl, aralkyl, cycloalkenyl,cycloalkyl, alkoxy, and acyl ##STR82## where R' is aryl, alkyl orcycloalkyl. x₁ and x₂ are integers from one to four, and the sum of x₁and x₂ does not exceed six.

The polycyclic phenol phenol is one having at least two aromatic nucleilinked by a polyvalent linking radical, as defined by the formula:##STR83## wherein Y is a polyvalent linking group selected from thegroup consisting of oxygen; carbonyl; sulfur; sulfinyl; aromatic,aliphatic and cycloaliphatic hydrocarbon groups; and oxyhydrocarbon,thiohydrocarbon and heterocyclic groups. The linking group can have fromone up to twenty carbon atoms.

Ar is a phenolic nucleus which can be a phenyl or a polycarbocyclicgroup having condensed or separate phenyl rings; each Ar group containsat least one free phenolic hydroxyl group up to a total of five. The Arrings can also include additional rings connected by additional linkingnuclei of the type Y, for example, Ar--Y--AR--Y--Ar.

m₁ and m₂ are numbers from one to five, and n₁ and n₂ are numbers of oneor greater, and preferably from one to four.

The aromatic nucleus Ar can, in addition to phenolic hydroxyl groups,include one or more inert substituents. Examples of such inertsubstituents include hydrogen, halogen atoms, e.g., chlorine, bromineand fluorine; organic radicals containing from one to about thirtycarbon atoms, such as alkyl, aryl, alkaryl, aralkyl, cycloalkenyl,cycloalkyl, alkoxy, aryloxy and acyloxy ##STR84## where R' is aryl,alkyl or cycloalkyl, or thiohydrocarbon groups having from one to aboutthirty carbon atoms, and carboxyl ##STR85## groups. Usually, however,each aromatic nucleus will not have more than about eighteen carbonatoms in any hydrogen substituent group. The Ar group can have from oneto four substituent groups per nucleus.

Typical aromatic nuclei include phenyl, naphthyl, phenanthryl,triphenylenyl, anthracenyl, pyrenyl, chrysenyl, and fluoroenyl groups.

When Ar is a benzene nucleus, the polyhydric polycyclic phenol has thestructure: ##STR86## wherein R₁, R₂ and R₃ are inert substituent groupsas described in the previous paragraph;

m₁ and m₃ are integers from one to a maximum of five;

m₂ is an integer from one to a maximum of four;

x₁ and x₃ are integers from zero to four, and

x₂ is an integer from zero to three;

y₁ is an integer from zero to about six and

y₂ is an integer from one to five, preferably one or two.

Preferably, the hydroxyl groups are located ortho and/or para to Y.

Exemplary Y groups are alkylene, alkylidene, and alkenylene; arylene,alkyl arylene, arylalkylene; cycloalkylene, cycloalkylidene; and oxa-and thia-substituted such groups; tetrahydrofuranes, esters and triazinogroups. The Y groups are usually bi, tri, or tetravalent, connectingtwo, three or four Ar groups. However, higher valency Y groupsconnecting more than four Ar groups, can also be used. According totheir constitution, the Y groups can be assigned to subgenera asfollows:

(1) Y groups where at least one carbon in a chain or cyclic arrangementconnect the aromatic groups, such as: ##STR87##

(2) Y groups where only atoms other than carbon link the aromatic rings,such as --O--, --S--, ##STR88## and --(S)_(x) -- where x is a numberfrom one to ten;

(3) Y groups made up of more than a single atom including both carbonand other atoms linking the aromatic nuclei, such as: ##STR89##

Although the relation of effectiveness to chemical structure isinsufficiently understood, many of the most effective phenols have Ygroups of subgenus (1), and accordingly this is preferred. Some of thesephenols can be prepared by the alkylation of phenols or alkyl phenolswith polyunsaturated hydrocarbons such as dicyclopentadiene orbutadiene.

Representative phenols include guaiacol, resorcinol monoacetate,vanillin, butyl salicylate, 2,6-di-tert-butyl-4-methyl phenol,2-tert-butyl-4-methoxy phenol, 2,4-dinonyl phenol, 2,3,4,5-tetradecylphenol, tetrahydro-α-naphthol, o-, m- and p-cresol, o-, m- andp-phenylphenol, o-, m- and p-xylenols, the carvenols, symmetricalxylenol, thymol, o-, m- and p-nonylphenol, o-, m- and p-dodecyl-phenol,and o-, m- and p-octyl-phenol, o-, and m-tert-butyl-p-hydroxy-anisole,p-n-decyloxy-phenol, p-n-decyloxy-cresol, nonyl-n-decyloxy-cresol,eugenol, isoeugenol, glyceryl monosalicylate,methyl-p-hydroxy-cinnamate, 4-benzoyloxy-phenol, p-acetylaminophenol,p-stearyl-aminophenol, methyl-p-hydroxybenzoate,p-di-chlorobenzoyl-aminophenol, p-hydroxysalicyl anilide,stearyl-(3,5-di-methyl-4-hydroxy-benzyl)thioglycolate,stearyl-β-(4-hydroxy-3,5-di-t-butylphenyl)propionate,distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, and distearyl(4-hydroxy-3-methyl-5-t-butyl)benzylmalonate.

Exemplary polyhydric phenols are orcinol, propyl gallate, catechol,resorcinol, 4-octyl-resorcinol, 4-dodecyl-resorcinol,4-octadecyl-catechol, 4-isooctyl-phloroglucinol, pyrogallol,hexahydroxybenzene, 4-isohexylcatechol,2,6-di-tertiary-butyl-resorcinol, 2,6-di-isopropyl-phloroglucinol.

Exemplary polyhydric polycyclic phenols are methylenebis-(2,6-di-tertiary-butyl-phenol), 2,2-bis-(4-hydroxy phenyl)-propane,methylene-bis-(p-cresol), 4,4'-benzylidene bis(2-tertiary-butyl-5-methyl-phenol), 4,4'-cyclo-hexylidenebis-(2-tertiary-butylphenol),2,2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)-phenol),2,6-bis-(2'-hydroxy-3'-tertiary-butyl-5'-methylbenzyl)-4-methylphenol,4,4'-bis-(2-tertiary-butyl-5-methyl-phenol),2,2'-bis-(4-hydroxy-phenyl)butane, ethylene bis-(p-cresol),4,4'-oxobis-phenol, 4,4'-oxobis-(3-methyl-5-isopropyl-phenol),4,4'-oxobis-(3-methyl-phenol), 2,2'-oxobis-(4-dodecyl-phenol),2,2'-oxobis-(4-methyl-5-tertiary-butyl-phenol), 4,4'-thio-bis-phenol;4,4'-thio-bis-(3-methyl-6-tertiary-butyl-phenol),2,2'-thio-bis-(4-methyl-6-tertiary-butyl-phenol),4,4'-n-butylidene-(2-t-butyl-5-methyl-phenol),2,2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)-phenol),4,4'-cyclohexylene bis-(2-tertiary-butyl-phenol),2,6-bis-(2'-hydroxy-3'-t-butyl-5'-methyl-benzyl)-4-methyl-phenol,4,4'-oxobis(naphthalene-1,5-diol),1,3'-bis-(naphthalene-2,5-diol)propane, and 2,2'-butylenebis-(naphthalene-2,7-diol),(3-methyl-5-tert-butyl-4-hydroxyphenyl)-4'-hydroxy-phenyl)propane,2,2'-methylene-bis-(4-methyl-5-isopropylphenol),2,2'-methylene-bis-(4-methyl-5-isopropylphenol),2,2'-methylene-bis-(5-tert-butyl-4-chlorophenol),(3,5-di-tert-butyl-4-hydroxyphenyl)-(4'-hydroxyphenyl)ethane,(2-hydroxy-phenyl)-(3',5'-di-tert-butyl-4',4-hydroxyphenyl)ethane,2,2'-methylene-bis-(4-octylphenol),4,4'-propylene-bis-(2-tert-butyl-phenol),2,2'-isobutylene-bis-(4-nonylphenol),2,4-bis-(4-hydroxy-3-t-butyl-phenoxy)-6-(n-octylthio)-1,3,5-triazine,2,4,6-tris-(4-hydroxy-3-t-butyl-phenoxy)-1,3,5-triazine,2,2'-bis-(3-t-butyl-4-hydroxyphenyl)thiazolo-(5,4-d)thiazole,2,2'-bis-(3-methyl-5-t-butyl-4-hydroxyphenyl)thiazolo-(5,4-d)-thiazole4,4'-bis-(4-hydroxyphenyl)pentanoic acid octadecyl ester,cyclopentylene-4,4'-bis-phenol, 2-ethylbutylene-4,4'-bisphenol,4,4'-cyclooctylene-bis-(2-cyclohexylphenol),β,β-thiodiethanol-bis-(3-tert-butyl-4-hydroxyphenoxy acetate),1,4-butanedio-bis-(3-tert-butyl-4-hydroxyphenoxy acetate),pentaerythritol tetra-(4-hydroxyphenol propionate), 2,4,4'-tri-hydroxybenzophenone, bis-(2-tert-butyl-3-hydroxy-5-methylphenyl)sulfide,bis-(2-tert-butyl-4-hydroxy-5-methylphenyl)sulfide,bis-(2-tert-butyl-4-hydroxy-5-methylphenyl)sulfoxide,bis-(3-ethyl-5-tert-butyl-4-hydroxybenzyl)sulfide,bis-(2-hydroxy-4-methyl-6-tert-butyl-phenyl)sulfide,4,4'-bis-(4-hydroxyphenol)pentanoic acid octadecyl thiopropionate ester,1,1,3-tris-(2'-methyl-4-hydroxy-5'-tert-butylphenyl)butane,1,1,3-tris-(1-methyl-3-hydroxy-4-tert-butylphenyl)butane,1,8-bis-(2-hydroxy-5-methylbenzoyl-n-octane,2,2'-ethylene-bis-[4'-(3-tert-butyl-4-hydroxyphenyl)-thiazole],1-methyl-3-(3-methyl-5-tert-butyl-4-hydroxybenzyl)-naphthalene, 2,2'-(2-butene)-bis-(4-methoxy-6-tert-butylphenol)-bis-[3,3-bis-(4-hydroxy-3-t-butylphenyl)butyricacid]glycol ester, 4,4'-butylidene-bis-(6-t-butyl-n-cresol),1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane,1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxyethylisocyanurate,2-octylthio-4,6-di-(4-hydroxy-3,5-di-t-butyl)phenoxy-1,3,5-triazine,4,4'-thiobis-(6-t-butyl-m-cresol) and pentaerythritol hydroxyphenylpropionate.

A particularly desirable class of polyhydric polycyclic phenols are thedicyclopentadiene polyphenols, which are of the type: ##STR90## in whichR₁ and R₂ are lower alkyl, and can be the same or different, and

n is the number of the groups enclosed by the brackets, and is usuallyfrom 1 to about 5.

These are described in U.S. Pat. No. 3,567,683, dated Mar. 2, 1971 toSpacht. A commerically available member of this class is Wingstay L,exemplified by dicyclopentadiene tri-(2-tert-butyl-4-methyl-phenol) ofthe formula: ##STR91##

The polyhydric polycyclic phenols used in the invention can also becondensation products of phenols or alkylphenols with hydrocarbonshaving a bicyclic ring structure and a double bond or two or more doublebonds, such as α-pinene, β-pinene, dipentene, limonene,vinylcyclohexene, dicyclopentadiene, allo-ocimene, isoprene andbutadiene. These condensation products are usually obtained under acidicconditions in the form of more or less complex mixtures of monomeric andpolymeric compounds. However, it is usually not necessary to isolate theindividual constituents. The entire reaction product, merely freed fromthe acidic condensation catalyst and unchanged starting material, can beused with excellent results. While the exact structure of these phenoliccondensation products is uncertain, the Y groups linking the phenolicnuclei all fall into the preferred subgenus 1. For method ofpreparation, see e.g., U.S. Pat. No. 3,124,555, U.S. Pat. No. 3,242,135,and British Pat. No. 961,504.

When the stabilizer composition is used in conjunction with a polyvalentmetal salt of an organic acid, the organic acid will ordinarily havefrom about six to about twenty-four caarbon atoms. The polyvalent metalcan be any metal of Group II of the Periodic Table, such as zinc,calcium, cadmium, barium, magnesium and strontium. The alkali metalsalts and heavy metal salts such as lead salts are unsatisfactory. Theacid can be any organic non-nitrogenous monocarboxylic acid having fromsix to twenty-four carbon atoms. The aliphatic, aromatic, alicyclic andoxygen-containing heterocyclic organic acids are operable as a class. Bythe term "aliphatic acid" is meant any open chain carboxylic acid,substituted, if desired, with nonreactive groups, such as halogen,sulfur and hydroxyl. By the term "alicyclic" it will be understood thatthere is intended any cyclic acid in which the ring is nonaromatic andcomposed solely of carbon atoms, and such acids may if desired haveinert, nonreactive substituents such as halogen, hydroxyl, alkylradicals, alkenyl radicals and other carbocyclic ring structurescondensed therewith. The oxygen-containing heterocyclic compounds can bearomatic or nonaromatic and can include oxygen and carbon in the ringstructure, such as alkyl-substituted furoic acid. The aromatic acidslikewise can have nonreactive ring substituents such as halogen, alkyland alkenyl groups, and other saturated or aromatic rings condensedtherewith.

As exemplary of the acids which can be used in the form of their metalsalts there can be mentioned the following: hexoic acid, 2-ethylhexoicacid, n-octoic acid, isooctoic acid, capric acid, undecylic acid, lauricacid, myristic acid, palmitic acid, margaric acid, stearic acid, oleicacid, ricinoleic acid, behemic acid, chlorocaproic acid, hydroxy capricacid, benzoic acid, phenylacetic acid, butyl benzoic acid, ethyl benzoicacid, propyl benzoic acid, hexyl benzoic acid, salicylic acid, naphthoicacid, 1-naphthalene acetic acid, orthobenzoyl benzoic acid, naphthenicacids derived from petroleum, abietic acid, dihydroabietic acid,hexahydrobenzoic acid, and methyl furoic acid.

The water-insoluble salts are preferred, because they are not leachedout when the plastic is in contact with water. Where these salts are notknown, they are made by the usual types of reactions, such as by mixingthe acid, or anhydride with the corresponding oxide or hydroxide of themetal in a liquid solvent, and heating, if necessary, until saltformation is complete.

A variety of organic triphosphites and acid phosphites can be employed,of which the following are exemplary.

The organic triphosphite can be any organic phosphite having three ormore organic radicals attached to phosphorus through oxygen. The acidphosphite can be any organic phosphite having one or two organicradicals attached to phosphorus through oxygen. These radicals can bemonovalent radicals, in the case of the triphosphites, diphosphites andmonophisphites.

The organic triphosphites in which the radicals are monovalent radicalscan be defined by the formula: ##STR92## in which R₁, R₂ and R₃ areselected from the group consisting of alkyl, alkenyl, aryl, alkaryl,aralkyl, and cycloalkyl groups having from one to about thirty carbonatoms.

The acid phosphites are defined by the same formula, but one or two ofR₁, R₂ and R₃ is hydrogen or a cation of a metal or ammonium.

Also included are the organic triphosphites having a bivalent organicradical forming a heterocyclic ring with the phosphorus of the type:##STR93## in which R₄ is a bivalent organic radical selected from thegroup consisting of alkylene, arylene, aralkylene, alkarylene andcycloalkylene radicals having from two to about thirty carbon atoms, andR₅ is a monovalent organic radical as defined above in the case of R₁,R₂ and R₃ ;

R₅ is hydrogen or a cation, in the case of the acid phosphites.

Also useful organic triphosphites are mixed heterocyclic-open chainphosphites of the type: ##STR94##

More complex triphosphites are formed from trivalent organic radicals,of the type: ##STR95## in which R₆ is a trivalent organic radical of anyof the types of R₁ to R₅, inclusive, as defined above.

A particularly useful class of complex triphosphites are thetetraoxadiphosphaspiro undecanes of the formula: ##STR96## where R₁ andR₂ are selected from the group consisting of aryl, alkyl, aryloxyethyl,alkyloxyethyl, aryloxyethoxyethyl, alkyloxyethoxyethyl andalkyloxypolyethoxyethyl having from about 1 to about 30 carbon atoms.

In the case of the acid phosphites, one or both of R₁ and R₂ is alsohydrogen or a cation.

An especially preferred class of organic triphosphites and acidphosphites have a bicyclic aromatic group attached to phosphorus throughoxygen, with no or one or more phenolic hydroxyl groups on either orboth of the aromatic rings. These phosphites are characterized by theformula; ##STR97## in which

Ar is a mono or bicyclic aromatic nucleus and m is an integer of from 0to about 5. is one or a plurality of organic radicals as defined abovefor R₁ to R₆, taken singly or together in sufficient number to satisfythe valences of the two phosphite oxygen atoms.

One or both radicals is also hydrogen, in the case of the acidphosphites, and can include additional bicyclic aromatic groups of thetype (HO)_(m) --Ar.

The cation in the case of acid phosphites can be a metal, such as analkali metal, for instance, sodium, potassium or lithium; an alkalineearth metal, for instance, barium, calcium, or a nontoxic polyvalentmetal, such as magnesium, tin and zinc.

Usually, the triphosphites and acid phosphites will not have more thanabout sixty carbon atoms.

Exemplary triphosphites are monophenyl di-2-ethylhexyl phosphite,diphenyl mono-2-ethylhexyl phosphite, di-isooctyl monotolyl phosphite,tri-2-ethylhexyl phosphite, phenyl dicyclohexyl phosphite, phenyldiethyl phosphite, triphenyl phosphite, tricresyl phosphite,tri(dimethylphenyl) phosphite, trioctadecyl phosphite, triisooctylphosphite, tridodecyl phosphite, isooctyl diphenyl phosphite, diisooctylphenyl phosphite, tri(t-octylphenyl) phosphite, tri-(t-nonylphenyl)phosphite, benzyl methyl isopropyl phosphite, butyl dicresyl phosphite,isooctyl di(octylphenyl) phosphite, di(2-ethylhexyl)(isooctylphenyl)phosphite, tri (2-cyclohexylphenyl) phosphite), tri-α-naphthylphosphite, tri (phenylphenyl) phosphite, tri(2-phenylethyl) phosphite,ethylene phenyl phosphite, ethylene t-butyl phosphite, ethylene isohexylphosphite, ethylene isooctyl phosphite, ethylene cyclohexyl phosphite,2-phenoxy-1,3,2-dioxaphosphorinane, 2-butoxy-1,3,2-dioxyphosphorinane,2-octoxy-5,5-dimethyl-dioxaphosphorinane, and2-cyclohexyloxy-5,5-diethyl dioxaphosphorinane.

Exemplary pentaerythritol triphosphites are3,9-diphenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,6)-undecane(diphenyl-pentaerythritol diphosphite),3,9-di(decyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro (5,5)-undecane,3,9-di(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3-phenoxy-9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(methoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(lauryloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di-p-tolyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(methoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3-methoxyethyloxy-9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(ethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(butoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3-methoxyethyloxy-9-butoxy-ethyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(methoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di-(butoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(methoxyethoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane,3,9-di(methoxy(polyethoxy)ethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecanewhere the (polyethoxy) ethyloxy group has an average molecular weight of350),3,9-di(methoxy(polyethoxy)ethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane (where the(polyethoxy) ethyloxy group has an average molecular weight of 550).

Exemplary of the bis aryl triphosphites are:bis(4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol)) isooctyl phosphite,mono(4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol)) di-phenylphosphite, tri-(4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenol))phosphite, (4,4'-benzylidene-bis(2-tertiary-butyl-5-methyl-phenol))diphenyl phosphite, isooctyl 2,2'-bis(-parahydroxyphenyl) propanephosphite, decyl 4,4'-n-butylidene-bis (2-tertiary-butyl-5-methylphenol)phosphite, tri-4,4'-thio-bis (2-tertiary-butyl-5-methylphenol)phosphite,2-ethylhexyl-2,2'-methylene-bis(4-methyl-6,1'-methylcyclohexyl) phenolphosphite, tri(2,2'-bis(para-hydroxyphenyl) propane) phosphite,tri(4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol) phosphite,isooctyl-(2,6-bis(2'-hydroxy-3,5-dinonylbenzyl)-4-nonyl phenyl))phosphite,tetra-tridecyl-4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenyl)diphosphite, tetra-isooctyl-4,4'-thio-bis(2-tertiary-butyl-5-methylphenyl) diphosphite,2,2'-methylene-bis(4-methyl-6,1'-methyl cyclohexyl phenyl)polyphosphite, isooctyl-4,4'-isopropylidene-bis-phenyl polyphosphite,2-ethylhexyl-2,2'-methylene-bis(4-methyl-6,1'-methyl-cyclohexyl) phenyltriphosphite, tetra-tridecyl-4,4'-oxydiphenyl diphosphite,tetra-n-dodecyl-4,4'-n-butylidene bis (2-tertiary-butyl-5-methylphenyl)diphosphite, tetra-tridecyl-4,4'-isopropylidene bisphenyl diphosphite,hexa-tridecylbutane-1,1,3-tris(2'-methyl-5'-tertiary-butylphenyl-4')triphosphite.

Exemplary acid phosphites are di(phenyl) phosphite, monophenylphosphite, mono(diphenyl) phosphite, dicresyl phosphite,di-(o-isooctylphenyl) phosphite, di(p-ethylhexylphenyl) phosphite,di(p-t-octylphenyl) phosphite, di(dimethylphenyl) phosphite, di-n-butylphosphite, di-2-ethylhexyl phosphite, mono-2-ethylhexylphosphite,diisooctyl phosphite, monoisooctyl phosphite, monododecyl phosphite,2-ethylhexyl phenyl phosphite, 2-ethylhexyl-(n-octylphenyl) phosphite,monocyclohexyl phosphite, dicyclohexyl phosphite, di(2-cyclohexylphenyl) phosphite, di-α-naphthyl phosphite, diphenyl phenyl phosphite,di(diphenyl) phosphite, di-(2-phenyl ethyl) phosphite, dibenzylphosphite, monobenzyl phosphite, n-butyl cresyl phosphite and didodecylphosphite, cresyl phosphite, t-octylphenyl phosphite, ethylenephosphite, butyl cresyl phosphite, isooctyl monotolyl phosphite andphenyl cyclohexyl phosphite.

Exemplary of the bis aryl acid phosphites are:bis(4,4'-thio-bis(2-tertiary-butyl-5-methylphenol))phosphite,(4,4'-thio-bis(2-tertiary-butyl-5-methylphenol)) phenyl phosphite,bis(4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenol)) phosphite,mono(4,4'-benzylidene-bis(2-tertiary-butyl-5-methylphenol)) phosphite,mono(2,2'-bis-(parahydroxyphenyl) propane) phosphite,mono(4,4'-butylidene-bis(2-tertiary-butyl-5-methylphenol) phosphite,bis(4,4'-thio-bis(2-tertiary-butyl-5-methylphenol)) phosphite,mono-2-ethylhexyl-mono-2,2'-methylene-bis(4-methyl-6,1'-methylcyclohexyl)phenol phosphite, bis(2,2'-bis(para-hydroxyphenyl)propane)phosphite,monoisooctyl-mono(4,4'-thio-bis(2-tertiary-butyl-5-methylphenol))phosphite,isooctyl-(2,6-bis(2'-hydroxy-3,5-dinonylbenzyl)-4-nonylphenyl))phosphite,tri-tridecyl-4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenyl)diphosphite, triisooctyl-4,4'-thio-bis(2-tertiary-butyl-5-methylphenyl)diphosphite, bis(2,2'-methylene-bis(4-methyl-6,1'-methyl cyclohexylphenyl)) phosphite, isooctyl-4,4'-isoproylidene-bis-phenyl phosphite,monophenyl mono(2,2'-methylene-bis(4-methyl-6,1'-methyl-cyclohexyl))triphosphite, di-tridecyl-4,4'-oxydiphenyl diphosphite,di-n-dodecyl-4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenyl)diphosphite, di-tridecyl-4,4'-isopropylidene bisphenyl diphosphite,tetra-tridecylbutane-1,1,3-tris(2'-methyl-5-tertiary-butylphenyl-4)-triphosphite.

The thiodipropionic acid ester has the following formula:

    R.sub.1 OOCCH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 COOY

in which R₁ is an organic radical selected from the group consisting ofhydrocarbon radicals such as alkyl, alkenyl, aryl, cycloalkyl and mixedalkyl aryl and mixed alkyl cycloalkyl radicals; hydroxyalkyl andhydroxyalkyloxyalkylene radicals; and esters thereof with aliphaticcarboxylic acids; and Y is selected from the group consisting of (a)hydrogen, (b) a second R radical R₂, which can be the same as ordifferent from the R₁ radical, (c) a polymeric chain of nthiodipropionic acid ester units:

    --XO[OCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 COOXO].sub.n OCCH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 COOZ

where Z is hydrogen, R₂ or M, n is the number of thiodipropionic acidester units in the chain, and X is a bivalent hydrocarbon group of thetype of R₁, that is, alkylene, alkenylene, cycloalkylene, mixedalkylene-arylene and mixed alkylene-cycloalkylene radicals;hydroxyalkylene and hydroxyalkyloxyalkylene radicals; and esters thereofwith aliphatic carboxylic acids; the value of n can range upwards from0, but there is no upper limit on n except as is governed by the ratioof carbon atoms to sulfur atoms as stated below; and (d) a polyvalentmetal M of Group II of the periodic table such as zinc, calcium,cadmium, barium, magnesium and strontium.

The molecular weights of the R and Y radicals are taken such that withthe remainder of the molecule the thiodipropionic ester has a total offrom about ten to about sixty carbon atoms per sulfur atom.

Accordingly, the various thiodipropionic acid ester species comingwithin the above-designated categories within the general formula can bedefined as follows:

(a) R₁ OOCCH₂ CH₂ SCH₂ CH₂ COOH

(b) R₁ OOCCH₂ CH₂ SCH₂ CH₂ COOR₂

(c) R₁ O[OCCH₂ CH₂ SCH₂ CH₂ COOX--O]_(n) OCCH₂ CH₂ SCH₂ CH₂ COOZ (d) R₁OOCCH₂ CH₂ SCH₂ CH₂ COOM

In the above formulae R₁ and R₂, M, X and Z are the same as before andthe value of n₁ can range upwards from 1, but there is no upper limit onn₁ except as is imposed by the ratio of carbon atoms, as stated below.In the polymer (c), as in the other forms of thiodipropionic acidesters, the total number of carbon atoms per sulfur atom is within therange from about ten to about sixty.

The R radical of these esters is important in furnishing compatibilitywith the polymer. The Y radical is desirably a different radical, R₂ orM or a polymer, where R is rather low in molecular weight, so as tocompensate for this in obtaining the optimum compatibility andnonvolatility. Where Y is a metal, the thiodipropionic acid esterfurnishes the beneficial properties of the polyvalent metal salt whichis described above.

The aryl, alkyl, alkenyl, and cycloalkyl groups may, if desired, containinert, nonreactive substituents such as halogen and other carbocyclicand heterocyclic ring structures condensed therewith.

Typical R radicals are, for example, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, t-butyl, amyl, isoamyl, n-octyl, isooctyl, 2-ethylhexyl, t-octyl, decyl, dodecyl, octadecyl, allyl, hexenyl, linoleyl,ricinoleyl, oleyl, phenyl, xylyl, tolyl, ethylphenyl, naphthyl,cyclohexyl, benzyl, cyclopentyl, methylcyclohexyl, ethylcyclohexyl, andnaphthenyl, hydroxyethyl, hydroxypropyl, glyceryl, sorbityl,pentaerythrityl, and polyoxyalkylene radicals such as those derived fromdiethylene glycol, triethylene glycol, polyoxypropylene glycol,polyoxyethylene glycol, and polyoxypropyleneoxyethylene glycol, andesters thereof with any of the organic acids named below in thediscussion of the polyvalent metal salts, including in addition thoseorganic acids having from two to five carbon atoms, such as acetic,propionic, butyric and valeric acids.

Typical X radicals are alkylene radicals such as ethylene,tetramethylene, hexamethylene, decamethylene, alkyl-substituted alkyleneradicals such as 1,2-propylene, ##STR98## arylene radicals such asphenylene ##STR99## methylenephenylene ##STR100## dimethylene phenylene##STR101## and alicyclylene such as cyclohexylene ##STR102## andcyclopentylene ##STR103##

As exemplary of the thiodipropionic acid esters which can be used, therecan be mentioned the following: monolauryl thiodipropionic acid,dilauryl thiodipropionate, butyl stearyl thiodipropionate, 2-ethylhexyllauryl thiodipropionate, di-2-ethylhexyl-thiodipropionate, diisodecylthiodipropionate, isodecyl phenyl thiodipropionate, benzyl laurylthiodipropionate, benzyl phenyl thiodipropionate, the diester of mixedcoconut fatty alcohols and thiodipropionic acid, the diester of mixedtallow fatty alcohols and thiodipropionic acid, the acid ester of mixedcottonseed oil fatty alcohols and thiodipropionic acid, the acid esterof mixed soyabean oil fatty alcohols and thiodipropionic acid,cyclohexyl nonyl thiodipropionate, monooleyl thiodipropionic acid,hydroxyethyl lauryl thiodipropionate, monoglyceryl thiodipropionic acid,glyceryl monostearate monothiodipropionate, sorbityl isodecylthiodipropionate, the polyester of diethylene glycol and thiodipropionicacid, the polyester of triethylene glycol and thiodipropionic acid, thepolyester of hexamethylene glycol and thiodipropionic acid, thepolyester of pentaerythritol and thiodipropionic acid, the polyester ofoctamethylene glycol and thiodipropionic acid, the polyester ofp-dibenzyl alcohol and thiodipropionic acid, ethylbenzyl laurylthiodipropionate, strontium stearyl thiodipropionate, magnesium oleylthiodipropionate, calcium dodecylbenzyl thiodipropionate, andmono(dodecylbenzyl)thiodipropionic acid.

These esters are for the most part known compounds, but where they arenot available, they are readily prepared by esterification ofthiodipropionic acid and the corresponding alcohol.

Also useful are:

(1) Thioalkanoic acid amides of Tokuno et al. Japanese Pat. No.16,286/68 having the formula: ##STR104## R is alkyl of one to eightcarbon atoms, R₁ is alkyl of six to twenty-four carbon atoms, and R₂ isalkylene of one to six carbon atoms.

(2) Thioalkanoic acid amides of 1,3,5-triazines of Ozeki et al. JapanesePat. No. 20,366/68 having the formula: ##STR105## R is alkyl of eight toeighteen carbon atoms.

(3) Bis-thioalkanoic acid amides of Yamamoto et al. Japanese Pat. No.23,765/68 having the formula: ##STR106## R is alkyl of more than sixcarbon atoms, aryl or aralkyl.

(4) Bis-thioalkylanoic acid amides of Ozeki et al. Japanese Pat. No.26,184/69 having the formula: ##STR107## R is alkyl of twelve toeighteen carbon atoms, and R₁ is alkylene of one to ten carbon atoms,cycloalkylene, or arylene.

(5) Bis-alkylene thioalkanoic acid amides of Ozeki Japanese Pat. No.31,464/69 having the formula: ##STR108## R is alkyl of more than sixcarbon atoms, aryl, or aralkyl.

(6) Thioalkanoic acid amide derivatives of Minagawa et al. publishedJapanese application No. 106,484/74 having the formula: ##STR109## R ishydrocarbyl of one to twenty carbon atoms.

(7) Alkylene bis-thioalkanoic acid amides of U.S. Pat. No. 4,279,805 toOhzeki et al. patented July 21, 1981, having the general formula:##STR110## wherein: R₁ is alkyl having from one to about fifty carbonatoms;

R₂ is alkylene having from one to about three carbon atoms; and

R₃ is alkylene having from about two to about twelve carbon atoms.

β-Alkylthiopropionic acid esters having the general formula:

    R--S--C.sub.2 H.sub.4 COOR(R').sub.n

wherein:

R is alkyl of four to twenty carbon atoms;

n is a number from 1 to 6; and

R' is the residue of an alcohol having from one to six hydroxyl groups.

Pentaerythritol tetra dodecyl thio propionate is an example of thisgroup.

Other conventional light stabilizers can be employed, such ashydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-n-octoxy benzophenone, 2,4-dihydroxybenzophenone,benzotriazoles, such as 2(2-hydroxy-5-methylphenyl)benzotriazoles,2(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole,2(2-hydroxy-3-5-di-t-butylphenyl) 5-chlorobenzotriazole,2(2-hydroxy-3,5-di-t-amylphenyl)benzotriazole, benzoates such asphenylsalicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxyphenylbenzoate, nickel compounds such asnickel-2,2'-thiobis(4-t-octyl-phenolate),nickel-mono-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate,substituted acrylonitriles such asmethyl-α-cyano-β-methyl-β-(p-methoxyphenyl)acrylate and oxalic anilidessuch as N-2-ethyl phenyl-N'-2-ethoxy-5-t-butyl phenyl oxalic diamide,N-2-ethyl phenyl-N'-2-ethoxy phenyl oxalic diamide.

A sufficient amount of the stabilizer or combination is used to improvethe resistance of the synthetic polymer to deterioration in physicalproperties when exposed to heat and light, including, for example,discoloration, reduction in melt viscosity and embrittlement. Very smallamounts are usually adequate. Amounts within the range from about 0.001to about 5% total stabilizers including the hydrocarbyl(polyphenol)poly(piperidyl triazines) of the invention by weight of the polymer aresatisfactory. Preferably, from 0.01 to 3% is employed for optimumstabilization.

The stabilizer systems of the invention are readily rendered in solidparticulate form, comprising a blend of:

(a) hydrocarbyl(polyphenol)poly(piperidyl triazines) light stabilizer inan amount of from about 10 to about 35 parts by weight;

and optionally:

(b) a phenolic antioxidant in an amount from about 10 to about 35 partsby weight; and/or

(c) other heat or light stabilizers in an amount of from about 10 toabout 35 parts by weight.

The hydrocarbyl(polyphenol)poly(piperidyl triazines) light stabilizer ofthe invention can be employed in combination with phenolic antioxidantand/or other conventional heat and light stabilizers for the particularsynthetic polymer.

Thus, for example, in the case of polyvinyl chloride resins, otherpolyvinyl chloride resin heat stabilizers can be included, includingpolyvalent metal fatty acid salts such as barium and cadmium salts ofthe higher fatty acids; organotin compounds; and epoxy compounds; andorganic phosphites.

With polyolefin resins there can be employed fatty acid salts ofpolyvalent metals, and the higher fatty acid esters of thiodipropionicacids, such as, for example, dilauryl thiodipropionate.

With polyamide resin compositions, polyamide stabilizers such as coppersalts in combination with iodides and/or other phosphorus compounds andsalts of divalent manganese can be used.

With synthetic rubbers and acrylonitrile-butadienestyrene terpolymers,other antioxidants and polyvalent metal salts of the higher fatty acidscan be used.

In addition, other conventional additives for synthetic polymers, suchas plasticizers, lubricants, emulsifiers, anti-static agents,flame-proofing agents, pigments and fillers, can be employed.

The stabilizer or combination is incorporated in the polymer in suitablemixing equipment, such as a mill or a Banbury mixer. If the polymer hasa melt viscosity which is too high for the desired use, the polymer canbe worked until its melt viscosity has been reduced to the desired rangebefore addition of the stabilizer. Mixing is continued until the mixtureis substantially uniform. The resulting composition is then removed fromthe mixing equipment and brought to the size and shape desired formarketing or use.

The stabilized polymer can be worked into the desired shape, such as bymilling, calendering, extruding or injection molding or fiber-forming.In such operations, it will be found to have a considerably improvedresistance to reduction in melt viscosity during the heating, as well asa better resistance to discoloration and embrittlement on ageing andheating.

The following Examples represent preferred embodiments of syntheticpolymer compositions containing the stabilizers in accordance with theinvention.

EXAMPLES 1 TO 6

Polypropylene compositions were prepared using stabilizers of theinvention and two stabilizers of the prior art, having the followingformulation:

    ______________________________________                                        Ingredient          Parts by Weight                                           ______________________________________                                        Polypropylene       100                                                       Stearyl-β-(3,5-di-t-butyl-4-                                                                 0.2                                                       hydroxyphenyl) propionate                                                     Stabilizer as shown in Table I                                                                    0.3                                                       ______________________________________                                    

The compositions were thoroughly blended in a Brabender Plastograph, andthen compression-molded to sheets 0.3 mm thick. Pieces 2.5 cm² were cutoff from the sheets, and exposed to a high pressure mercury lamp, withand without immersion in hot water at 80° C. for 15 hours. The time inhours when degradation set in, as determined by a significantdiscoloration and/or embrittlement, was noted as hours to failure, andthe results are set forth in Table I.

    TABLE I      Hours to Failure   Without After Example No. Stabilizer Immersion     Immersion       Control 1 N,N'Bis(4,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-t     riazine-2-yl) hexamethylenediamine 450 310 Control 2 1,4-Bis(4,6-bis(N2,2     ,6,6-tetramethyl-4-piperidyl)butylamino)-1,3,5-triazine-2-yloxy) benzene     420 290      Example 1     ##STR111##      800 720      Example 2     ##STR112##      770 680      Example 3     ##STR113##      820 750      Example 4     ##STR114##      790 710           Example 5     ##STR115##      ##STR116##      820 760      Example 6     ##STR117##      ##STR118##      810 740

The improved stabilizing effectiveness of the compounds of the inventionas compared to the compounds of the prior art is apparent from the abovedata.

EXAMPLES 7 TO 12

Conventional stabilizers for polymeric materials may lose theireffectiveness because of volatilization or decomposition at the highpolymer processing temperatures. This is not true of the stabilizers ofthe invention, as shown by observing the effect of heat in repeatedextrusions of ethylene-propylene copolymer compositions.

The compositions were prepared using stabilizers of the invention andtwo stabilizers of the prior art, having the following formulation:

    ______________________________________                                        Ingredient          Parts by Weight                                           ______________________________________                                        Ethylene-propylene copolymer                                                                      100                                                       Ca stearate         0.2                                                       Stearyl-β-(3,5-di-t-butyl-4-                                                                 0.1                                                       hydroxyphenyl) propionate                                                     Dilaurylthiodipropionate                                                                          0.2                                                       Stabilizer as shown in Table II                                                                   0.2                                                       ______________________________________                                    

The compositions were mixed and then extruded 5 times at a cylindertemperature of 230° C. and 240° C., a head die temperature of 250° C.,and a velocity of 20 rpm. The test pieces were then molded by injectionmolding at 250° C. The test pieces were exposed to a high pressuremercury lamp. The time in hours when degradation set in, as determinedby a significant discoloration and/or embrittlement, was noted as hoursto failure, and the results are set forth in Table II.

    TABLE II      Hours to Failure   Extruded Extruded Example No. Stabilizer One Time     Five Times       Control 1 N,N'Bis(4,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-t     riazine-2-yl)hexamethylenediamine 420 290 Control 2 1,4-Bis(4,6-bis(N2,2,     6,6-tetramethyl-4-piperidyl)butylamino)-1,3,5-triazine-2-yloxy)benzene     450 280      Example 7     ##STR119##      600 530      Example 8     ##STR120##      580 500      Example 9     ##STR121##      620 560      Example 10     ##STR122##      600 540           Example 11     ##STR123##      ##STR124##      630 580      Example 12     ##STR125##      ##STR126##      650 590

The improved stabilizing effectiveness of the compounds of the inventionas compared to the compounds of the prior art is apparent from the abovedata.

EXAMPLES 13 TO 18

High density polyethylene compositions were prepared using thestabilizers of the invention and two of the prior art, having thefollowing formulation:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        High density polyethylene                                                                          100                                                      Ca stearate          1                                                        Tetrakis-(methylene-3-(3,5-di-t-                                                                   0.1                                                      butyl-4-hydroxyphenyl)propionate)                                             methane                                                                       Distearyl thiodipropionate                                                                         0.3                                                      Stabilizer as shown in Table III                                                                   0.2                                                      ______________________________________                                    

The stabilizers were blended with the polymer on a two-roll mill andsheets 0.5 mm thick were prepared by compression molding of the blend.Pieces 2.5 cm² were cut off from the sheets, and exposed in aWeather-O-Meter to ultraviolet light. The time in hours when degradationset in, as determined by a significant discoloration and/orembrittlement, was noted as hours to failure, and the results are setforth in Table III.

    TABLE III      Example No. Stabilizer Hours to Failure       Control 1 N,N'Bis(4,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-t     riazine-2-yl) hexamethylenediamine      730 Control 2 1,4-Bis(4,6-bis(N2,2,6,6-tetramethyl-4-piperidyl)butylamin     o)-1,3,5-triazine-2-yloxy) benzene  680      Example 13     ##STR127##      1070      Example 14     ##STR128##      1020      Example 15     ##STR129##      1100      Example 16     ##STR130##      1050          Example 17     ##STR131##      ##STR132##      1140      Example 18     ##STR133##      ##STR134##      1080

The improved stabilizing effectiveness of the compounds of the inventionas compared to the compounds of the prior art is apparent from the abovedata.

EXAMPLES 19 TO 23

Ethylene vinyl acetate copolymer compositions were prepared usingstabilizers of the invention and two stabilizers of the prior art,having the following formulation:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Ethylene-vinyl acetate copolymer                                                                   100                                                      2,6-Di-t-butyl-p-cresol                                                                            0.1                                                      Ca stearate          0.1                                                      Zn stearate          0.1                                                      Diisodecylphenyl phosphite                                                                         0.2                                                      Stabilizer as shown in Table IV                                                                    0.2                                                      ______________________________________                                    

The stabilizers were blended with the polymer on a two-roll mill at 130°C. Sheets 0.4 mm thick were then compression-molded at 140° C. from theresulting blend. Pieces 2.5 cm² were cut off from the sheets, andexposed to ultraviolet light in a Weather-O-Meter for 500 hours. Tensilestrength of the sheet samples was determined before and at theconclusion of the test. The results are shown in Table IV as percentretention of the initially-determined tensile strength.

    TABLE IV      Example No. Stabilizer % Retention of Tensile Strength       Control 1 N,N'Bis(4,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-t     riazine-2-yl)hexamethylenediamine 68 Control 2 1,4-Bis(4,6 bis(N2,2,6,6-t     etramethyl-4-piperidyl)butylamino)-1,3,5-triazine-2yloxy)benzene 64     Example 19      ##STR135##      78      Example 20     ##STR136##      75      Example 21     ##STR137##      79          Example 22     ##STR138##      ##STR139##      80      Example 23     ##STR140##      ##STR141##      82

The improved stabilizing effectiveness of the compounds of the inventionas compared to the compounds of the prior art is apparent from the abovedata.

EXAMPLES 24 TO 30

Polyvinyl chloride resin compositions were prepared having the followingformulation, utilizing stabilizers in accordance with the invention andstabilizers of the prior art:

    ______________________________________                                        Ingredient          Parts by Weight                                           ______________________________________                                        Polyvinyl chloride  100                                                       Dioctyl phthalate   48                                                        Epoxidized soybean oil                                                                            2                                                         Tris(nonylphenyl)phosphite                                                                        0.2                                                       Ca stearate         1.0                                                       Zn stearate         0.1                                                       Stabilizer as shown in Table V                                                                    0.3                                                       ______________________________________                                    

The stabilizers were mixed with the polyvinyl chloride on a two-rollmill and then sheeted off to form sheets 1 mm thick. The lightresistance of the sheets was determined by placing strips 1 cm wide in aWeather-O-Meter, and exposing them to ultraviolet light. The timerequired for the sheets to develop a noticeable discoloration and/orembrittlement, indicating deterioration due to oxidation in the presenceof ultraviolet light, was then noted in hours as the hours to failure.The following results were obtained.

    TABLE V      Example No. Stabilizer Hours to Failure       Control 1 N,N'Bis(4,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-t     riazine-2-yl)hexamethylenediamine 530 Control 2 1,4-Bis(4,6-bis(N2,2,6,6-     tetramethyl-4-piperidyl)butylamino)-1,3,5-triazine-2-yloxy)benzene 500     Example 24      ##STR142##      750      Example 25     ##STR143##      730      Example 26     ##STR144##      700      Example 27     ##STR145##      730       Example 28     ##STR146##      ##STR147##     780       Example 29     ##STR148##      ##STR149##     760       Example 30     ##STR150##      ##STR151##     720

The improved stabilizing effectiveness of the compounds of the inventionas compared to the compounds of the prior art is apparent from the abovedata.

EXAMPLES 31 TO 35

Acrylonitrile-butadiene-styrene terpolymer resin compositions wereprepared, using stabilizers of the invention and of the prior art, withthe following formulation:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Acrylonitrile-butadiene-styrene                                                                     100                                                     terpolymer                                                                    4,4-Butylidene-bis(2-t-butyl-m-cresol)                                                              0.1                                                     Stabilizer as shown in Table VI                                                                     0.3                                                     ______________________________________                                    

The stabilizers were blended with the resin on a two-roll mill, andsheets 3 mm thick were prepared by compression molding of the resultingblend. Pieces 2.5 cm² were cut off from the sheets and subjected toultraviolet light in a Weather-O-Meter for 800 hours. The tensilestrength of the strips was determined before and after the testexposure, and the results are reported in Table VI as the percent oftensile strength retained at the end of the test.

    TABLE VI      Example No. Stabilizer % Retention of Tensile Strength       Control 1 N,N'Bis(4,6 bis(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-t     riazine-2-yl)hexamethylenediamine 65 Control 2 1,4-Bis(4,6-bis(N2,2,6,6-t     etramethyl-4-piperidyl)butylamino)-1,3,5-triazine-2-yloxy)benzene 62     Example 31      ##STR152##      82      Example 32     ##STR153##      80      Example 33     ##STR154##      84          Example 34     ##STR155##      ##STR156##      84      Example 35     ##STR157##      ##STR158##      81

The improved stabilizing effectiveness of the compounds of the inventionas compared to the compounds of the prior art is apparent from the abovedata.

EXAMPLES 36 TO 41

Polyurethane resin compositions were prepared using stabilizers of theinvention and of the prior art, having the following formulation:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Polyurethane resin (Asahi Denka U-100)                                                              100                                                     Ba stearate           0.7                                                     Zn stearate           0.3                                                     2,6-di-t-butyl-p-cresol                                                                             0.1                                                     Stabilizer as shown in Table VII                                                                    0.3                                                     ______________________________________                                    

The stabilizers were blended with the finely powdered polyurethane resinon a two-roll mill for five minutes at 70° C., and then sheeted off. Thesheet was compression molded at 120° C. for 5 minutes to form sheets 0.5mm thick. Pieces 2.5 cm² were cut out from the sheets and exposed toultraviolet light in a Weather-O-Meter for fifty hours. Elongationbefore and after exposure was determined, and the percent elongationretained after the exposure is given in Table VII.

    TABLE VII      Example No. Stabilizer % Retention of Elongation       Control 1 N,N'Bis(4,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-t     riazine-2-yl) hexamethylenediamine 58 Control 2 1,4-Bis(4,6-bis(N 2,2,6,6     -tetramethyl-4-piperidyl)butylamino)-1,3,5-triazine-2-yloxy) benzene 60     Example 36      ##STR159##      74      Example 37     ##STR160##      71      Example 38     ##STR161##      75      Example 39     ##STR162##      70          Example 40     ##STR163##      ##STR164##      75      Example 41     ##STR165##      ##STR166##      77

The improved stabilizing effectiveness of the compounds of the inventionas compared to the compounds of the prior art is apparent from the abovedata.

EXAMPLES 42 TO 48

The stabilizers of this invention are effective light stabilizers forsynthetic polymer coating compositions, particularly acrylic lacquers.This is demonstrated by the following experiments.

The effect of the stabilizer in a two coat metallic effect finishcomprising metallic effect priming lacquer and unpigmented finishinglacquer was determined.

(a) Metallic effect priming lacquer

Methyl methacrylate, 100 g, n butyl acrylate, 66 g,2-hydroxyethyl-methacrylate, 30 g, methacrylic acid, 4 g, xylene, 80 g,and n-butanol, 20 g, were heated with stirring at 110° C. while adding asolution of azo-bis-isobutyronitrile, 2 g, dodecylmercaptan, 0.5 g,xylene, 80 g, and n-butanol, 20 g, added dropwise over 3 hours. Thesolution was then stirred an additional two hours at 110° C.

The resulting acrylic resin solution, 12 parts, was then made into ametallic effect priming lacquer by mixing it with butoxylated methylolmelamine (Mitsui Toatsu Co., Yuban 20SE60; solids content 60%) 2.5parts, cellulose acetobutyrate (20% butylacetate solution) 50 parts,aluminum pigment (Toyo Aluminum Co., Alpaste 1123N) 5.5 parts, xylene 10parts, butyl acetate, 20 parts, and copper phthalocyanine blue, 0.2part.

(b) Unpigmented finishing lacquer

An unpigmented finishing lacquer was then prepared by mixing 48 parts ofthe acrylic resin solution with butoxylated methylol melamine, 10 parts,xylene, 10 parts, butoxyethylacetate, 1 part, and the stabilizer shownin Table VIII, 0.15 part.

Pieces of steel sheeting which were coated with a primer were firstcoated with the priming lacquer and then with the finishing lacquer. Thepriming lacquer was sprayed on to a thickness of about 20μ and aired for10 minutes. Then the clear lacquer was sprayed on to a thickness ofabout 30μ. After airing for 15 minutes the samples were stoved for 30minutes at 140° C.

The coated sheets were exposed to ultraviolet light in aWeather-O-Meter. The time in hours when degradation set in, determinedby cracking on the surface of the sheet, was noted as hours to failure.The results are shown in Table VIII.

    TABLE VIII      Example No. Stabilizer Hours to Failure       Control 1 None 1600 Control 2 N,N'Bis(4,6-bis(2,2,6,6-tetramethyl-4-pip     eridylamino)-1,3,5-triazine-2-yl)hexamethylenediamine 2200 Control 3     1,4-Bis(4,6-bis(N2,2,6,6-tetramethyl-4-piperidyl)butylamino)-1,3,5-triazi     ne-2yloxy)benzene 2100 Example 42      ##STR167##      3300      Example 43     ##STR168##      3100      Example 44     ##STR169##      3400      Example 45     ##STR170##      3300          Example 46     ##STR171##      ##STR172##      3400      Example 47     ##STR173##      ##STR174##      3100      Example 48     ##STR175##      ##STR176##      3000

The improved stabilizing effectiveness of the compounds of the inventionas compared to the compounds of the prior art is apparent from the abovedata.

Having regard to the foregoing disclosure, the following is claimed asinventive and patentable embodiments thereof:
 1. A polyvinyl chlorideresin composition having improved resistance to deterioration uponexposure to light comprising a polyvinyl chloride resin formed at leastin part of the recurring group: ##STR177## and having a chlorine contentin excess of 40%, where X is either hydrogen or chlorine; and ahydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethylpiperidyl-1,3,5-triazine) having the formula: ##STR178## in which: R isa hydrocarbyl group having the valence n;R₁ is selected from the groupconsisting of hydrogen; alkyl, alkenyl, cycloalkyl, hydroxyalkyl andalkoxy having from one to about twelve carbon atoms; acyl having fromabout one to about twelve carbon atoms; and oxyl; Y is selected from thegroup consisting of ##STR179## wherein R₄ is lower alkyl having from oneto about six carbon atoms; R₅ is selected from the group consisting ofhydrogen; alkyl, hydroxy alkyl and alkoxy having from one to abouttwelve carbon atoms; and cycloalkyl having from three to about twelvecarbon atoms; and ##STR180## X is selected from the group consisting of##STR181## wherein: R₆ is selected from the group consisting of alkyl,hydroxyalkyl and alkylenealkoxy having from one to about twelve carbonatoms; cycloalkyl having from three to about twelve carbon atoms; andaryl having from six to about eighteen carbon atoms;R₇ and R₈ areselected from the group consisting of hydrogen; alkyl having from one toabout twelve carbon atoms; cycloalkyl having from three to about twelvecarbon atoms; and aryl having from six to about eighteen carbon atoms;and R₇ and R₈ taken together as alkylene in a five to six member ringincluding the nitrogen atom in the ring; R₂ and R₃ are selected from thegroup consisting of hydrogen and lower alkyl having from one to aboutsix carbon atoms; and n is a number from 2 to
 4. 2. A polyvinyl chlorideresin composition in accordance with claim 1 in which the polyvinylchloride resin is polyvinyl chloride homopolymer.
 3. A polyvinylchloride resin composition in accordance with claim 1 in which thepolyvinyl chloride resin is a copolymer of vinyl chloride and vinylacetate.
 4. An olefin polymer composition having improved resistance todeterioration upon exposure to light comprising an olefin polymerselected from the group consisting of polymers of alpha-olefins havingfrom two to six carbon atoms and polystyrene, and ahydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethylpiperidyl-1,3,5-triazine) having the formula: ##STR182## in which: R isa hydrocarbyl group having the valence n;R₁ is selected from the groupconsisting of hydrogen; alkyl, alkenyl, cycloalkyl, hydroxyalkyl andalkoxy having from one to about twelve carbon atoms; acyl having fromabout one to about twelve carbon atoms; and oxyl; Y is selected from thegroup consisting of ##STR183## wherein R₄ is lower alkyl having from oneto about six carbon atoms; R₅ is selected from the group consisting ofhydrogen; alkyl, hydroxy alkyl and alkoxy having from one to abouttwelve carbon atoms; and cycloalkyl having from three to about twelvecarbon atoms; and ##STR184## X is selected from the group consisting of##STR185## wherein: R₆ is selected from the group consisting of alkyl,hydroxyalkyl and alkylenealkoxy having from one to about twelve carbonatoms; cycloalkyl having from three to about twelve carbon atoms; andaryl having from six to about eighteen carbon atoms;R₇ and R₈ areselected from the group consisting of hydrogen; alkyl having from one toabout twelve carbon atoms; cycloalkyl having from three to about twelvecarbon atoms; and aryl having from six to about eighteen carbon atoms;and R₇ and R₈ taken together as alkylene in a five to six member ringincluding the nitrogen atom in the ring; R₂ and R₃ are selected from thegroup consisting of hydrogen and lower alkyl having from one to aboutsix carbon atoms; and n is a number from 2 to
 4. 5. An olefin polymercomposition in accordance with claim 4 wherein the polyolefin ispolypropylene.
 6. An olefin polymer composition in accordance with claim4 wherein the polyolefin is polyethylene.
 7. An olefin polymercomposition in accordance with claim 4 wherein the polyolefin isethylene-propylene copolymer.
 8. An acrylonitrile-butadiene-styrenepolymer having improved resistance to deterioration upon exposure tolight comprising an acrylonitrile-butadiene-styrene polymer and ahydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethylpiperidyl-1,3,5-triazine) having the formula: ##STR186## in which: R isa hydrocarbyl group having the valence n;R₁ is selected from the groupconsisting of hydrogen; alkyl, alkenyl, cycloalkyl, hydroxyalkyl andalkoxy having from one to about twelve carbon atoms; acyl having fromabout one to about twelve carbon atoms; and oxyl; Y is selected from thegroup consisting of ##STR187## wherein R₄ is lower alkyl hving from oneto about six carbon atoms; R₅ is selected from the group consisting ofhydrogen; alkyl, hydroxy alkyl and alkoxy having from one to abouttwelve carbon atoms; and cycloalkyl having from three to about twelvecarbon atoms; and ##STR188## X is selected from the group consisting of##STR189## wherein: R₆ is selected from the group consisting of alkyl,hydroxyalkyl and alkylenealkoxy having from one to about twelve carbonatoms; cycloalkyl having from three to about twelve carbon atoms; andaryl having from six to about eighteen carbon atoms;R₇ and R₈ areselected from the group consisting of hydrogen; alkyl having from one toabout twelve carbon atoms; cycloalkyl having from three to about twelvecarbon atoms; and aryl having from six to about eighteen carbon atoms;and R₇ and R₈ taken together as alkylene in a five to six member ringincluding the nitrogen atom in the ring; R₂ and R₃ are selected from thegroup consisting of hydrogen and lower alkyl having from one to aboutsix carbon atoms; and n is a number from 2 to
 4. 9. An ethylene-vinylacetate copolymer having improved resistance to deterioration uponexposure to light comprising an ethylene-vinyl acetate copolymer and ahydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethylpiperidyl-1,3,5-triazine) having the formula: ##STR190## in which: R isa hydrocarbyl group having the valence n;R₁ is selected from the groupconsisting of hydrogen; alkyl, alkenyl, cycloalkyl, hydroxyalkyl andalkoxy having from one to about twelve carbon atoms; acyl having fromabout one to about twelve carbon atoms; and oxyl; Y is selected from thegroup consisting of ##STR191## wherein R₄ is lower alkyl having from oneto about six carbon atoms; R₅ is selected from the group consisting ofhydrogen; alkyl, hydroxy alkyl and alkoxy having from one to abouttwelve carbon atoms; and cycloalkyl having from three to about twelvecarbon atoms; and ##STR192## X is selected from the group consisting of##STR193## wherein: R₆ is selected from the group consisting of alkyl,hydroxyalkyl and alkylenealkoxy having from one to about twelve carbonatoms; cycloalkyl having from three to about twelve carbon atoms; andaryl having from six to about eighteen carbon atoms;R₇ and R₈ areselected from the group consisting of hydrogen; alkyl having from one toabout twelve carbon atoms; cycloalkyl having from three to about twelvecarbon atoms; and aryl having from six to about eighteen carbon atoms;and R₇ and R₈ taken together as alkylene in a five to six member ringincluding the nitrogen atom in the ring; R₂ and R₃ are selected from thegroup consisting of hydrogen and lower alkyl having from one to aboutsix carbon atoms; and n is a number from 2 to
 4. 10. A polyurethanehaving improved resistance to deterioration upon exposure to lightcomprising a polyurethane and ahydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethylpiperidyl-1,3,5-triazine) having the formula: ##STR194## in which: R isa hydrocarbyl group having the valence n;R₁ is selected from the groupconsisting of hydrogen; alkyl, alkenyl, cycloalkyl, hydroxyalkyl andalkoxy having from one to about twelve carbon atoms; acyl having fromabout one to about twelve carbon atoms; and oxyl; Y is selected from thegroup consisting of ##STR195## wherein R₄ is lower alkyl having from oneto about six carbon atoms; R₅ is selected from the group consisting ofhydrogen; alkyl, hydroxy alkyl and alkoxy having from one to abouttwelve carbon atoms; and cycloalkyl having from three to about twelvecarbon atoms; and ##STR196## X is selected from the group consisting of##STR197## wherein: R₆ is selected from the group consisting of alkyl,hydroxyalkyl and alkylenealkoxy having from one to about twelve carbonatoms; cycloalkyl having from three to about twelve carbon atoms; andaryl having from six to about eighteen carbon atoms;R₇ and R₈ areselected from the group consisting of hydrogen; alkyl having from one toabout twelve carbon atoms; cycloalkyl having from three to about twelvecarbon atoms; and aryl having from six to about eighteen carbon atoms;and R₇ and R₈ taken together as alkylene in a five to six member ringincluding the nitrogen atom in the ring; R₂ and R₃ are selected from thegroup consisting of hydrogen and lower alkyl having from one to aboutsix carbon atoms; and n is a number from 2 to 4.